WO2021192822A1 - Resin composition for semiconductor encapsulation, and semiconductor device - Google Patents

Abstract

Provided are a resin composition for semiconductor encapsulation with a sufficiently reduced specific permittivity, and a semiconductor device resin-sealed using the resin composition for semiconductor encapsulation. This resin composition for semiconductor encapsulation comprises (A) an epoxy resin, (B) a phenol resin curing agent, (C) a curing promoter, (D) an inorganic filler, and (E) resin particles, wherein the resin particles (E) are formed from a resin containing a structural unit derived from a cyclic olefin compound represented by general formula (1) below.

Description

Resin composition for encapsulating semiconductors and semiconductor devices

The present disclosure relates to a resin composition for encapsulating a semiconductor and a semiconductor device.

Conventionally, resin-sealed semiconductor devices have been widely used together with ceramic-sealed semiconductor devices. This resin-sealed semiconductor device is formed by resin-molding semiconductor elements such as transistors, ICs, and LSIs by transfer molding using a sealing material such as an epoxy resin composition. It is excellent in terms of low price.

However, in recent years, semiconductor elements such as microprocessors have been improved in functionality and performance, and based on this, the operating frequency tends to increase further. Further, in the information and communication related fields, especially in small electronic devices such as mobile phones and PHS, a frequency band close to gigahertz is being used in terms of the frequency band, and a two-digit gigahertz band is further used. Currently, the communication to be used is also under development.

As described above, in the situation where the high frequency of the semiconductor element is increasing, the development of a low dielectric constant epoxy resin composition for molding used in the resin-sealed semiconductor device corresponding to the high frequency of the semiconductor element is required.
Under such circumstances, for example, a resin composition containing a dihydroxybenzoxazine resin (Patent Document 1), a resin composition containing fluororesin particles whose surface is coated with fine inorganic particles (Patent Document 2), and a spherical hexagonal crystal. A resin composition containing tickerboron (Patent Document 3) and the like have been studied.

Japanese Unexamined Patent Publication No. 2000-154225 Japanese Unexamined Patent Publication No. 2001-40182 Japanese Unexamined Patent Publication No. 2005-314568

However, the relative permittivity of none of the above-disclosed resin compositions was sufficiently low. Therefore, it has been strongly desired to develop a resin composition for semiconductor encapsulation in which the relative permittivity is sufficiently reduced.

The present inventor has a semiconductor in which the relative permittivity is sufficiently reduced by using a resin composition for encapsulating a semiconductor containing (E) resin particles composed of a polymer containing a structural unit derived from a predetermined cyclic olefin compound. It has been found that a resin composition for encapsulation can be obtained.
The present disclosure has been completed based on such findings.

That is, the disclosure of the present application relates to the following.
[1] Containing (A) epoxy resin, (B) phenol resin curing agent, (C) curing accelerator, (D) inorganic filler, and (E) resin particles, the (E) resin particles are generally described below. A resin composition for encapsulating a semiconductor, which comprises a resin containing a structural unit derived from a cyclic olefin compound represented by the formula (1).

(In the general formula (1), R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and are R ⁹ and R. ¹⁰ , R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² are bonded to each other to form a ring. Further, n represents 0 or a positive integer, and when n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit.)
[2] The resin composition for semiconductor encapsulation according to the above [1], wherein the content of the resin particles (E) in the resin composition for encapsulating a semiconductor is 5% by mass or more and 20% by mass or less.
[3] The resin composition for semiconductor encapsulation according to the above [1] or [2], wherein the average particle size of the resin particles (E) is 0.1 μm or more and 50 μm or less.
[4] The above-mentioned [1] to [3], wherein the resin particles (E) are particles obtained by classifying and pulverizing a resin containing a structural unit derived from the cyclic olefin compound at 10 ° C. or lower. Resin composition for encapsulating semiconductors.
[5] The semiconductor seal according to any one of [1] to [4] above, wherein the content of the epoxy resin (A) in the resin composition for encapsulating a semiconductor is 5% by mass or more and 20% by mass or less. Epoxy composition for stopping.
[6] The semiconductor according to any one of [1] to [5] above, wherein the content of the inorganic filler (D) in the resin composition for encapsulating a semiconductor is 60% by mass or more and 90% by mass or less. Resin composition for sealing.
[7] The resin composition for semiconductor encapsulation according to the above [1] to [6], further comprising a low stress material (F).
[8] Any of the above [1] to [7], wherein the content of the low stress material (F) in the semiconductor encapsulating resin composition is 0.1% by mass or more and 1.5% by mass or less. The resin composition for encapsulating a semiconductor according to.
[9] The (G) benzoxazine resin further comprises (G) benzoxazine resin, and the (G) benzoxazine resin is the compound represented by the following general formula (2), according to any one of the above [1] to [8]. Resin composition for encapsulating semiconductors.

(In the general formula (2), X ¹ is an alkylene group having 1 to 10 carbon atoms, a group represented by the following general formula (3), -SO _2- , -CO-, an oxygen atom, or a single bond. R is a hydrogen atom or a hydrocarbon group having 1 or more and 10 or less carbon atoms, respectively.)

(In the general formula (3), X ² is a hydrocarbon group having an aromatic ring and having 6 or more and 30 or less carbon atoms, and m is an integer of 0 or 1 or more.)
[10] The semiconductor encapsulating resin according to the above [9], wherein the content of the (G) benzoxazine resin is 0 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the (A) epoxy resin. Composition.
[11] The total content of the (E) resin particles and the (G) benzoxazine resin in the semiconductor encapsulating resin composition is 5% by mass or more and 30% by mass or less. 10] The resin composition for encapsulating a semiconductor.
[12] A semiconductor device for encapsulating a semiconductor element using the resin composition for encapsulating a semiconductor according to any one of the above [1] to [11].

According to the present disclosure, it is possible to provide a semiconductor encapsulating resin composition having a sufficiently reduced relative permittivity, and a resin-encapsulated semiconductor device using the semiconductor encapsulating resin composition.

Hereinafter, the present disclosure will be described in detail with reference to one embodiment.
In the present specification, the "average particle size" means, for example, a particle size (d50) at which the integrated volume becomes 50% in the particle size distribution measured by a laser diffraction type particle size distribution measuring device.

[Resin composition for semiconductor encapsulation]
The resin composition for encapsulating a semiconductor of the present embodiment (hereinafter, also simply referred to as “resin composition”) includes (A) an epoxy resin, (B) a phenol resin curing agent, (C) a curing accelerator, and ( It contains (D) an inorganic filler and (E) resin particles, and further contains (F) a low-stress material, (G) a benzoxazine resin, and (H) other components (additives), if necessary.

((A) Epoxy resin)
The epoxy resin (A) used in the present embodiment is not particularly limited, and examples thereof include an epoxy resin having two or more epoxy groups in one molecule, which may be a monomer, an oligomer, or a polymer. You may.
Specific examples of the (A) epoxy resin include crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol type epoxy resin, and stillben type epoxy resin; novolak type epoxy such as phenol novolac type epoxy resin and cresol novolac type epoxy resin. Resin: Polyfunctional epoxy resin such as triphenol methane type epoxy resin and alkyl-modified triphenol methane type epoxy resin; phenol aralkyl type epoxy resin having a phenylene skeleton, phenol aralkyl type epoxy resin containing biphenylene skeleton (hereinafter, "biphenyl aralkyl type epoxy") Aralkyl type epoxy resin such as "resin"); naphthol type epoxy resin such as dihydroxynaphthalene type epoxy resin and epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene dimer; triglycidyl isocyanurate, monoallyl Examples thereof include triazine nuclei-containing epoxy resins such as diglycidyl isocyanurate; and bridged cyclic hydrocarbon compound-modified phenol-type epoxy resins such as dicyclopentadiene-modified phenol-type epoxy resins. One of these may be used alone, or two or more thereof may be used in combination.
Among these, from the viewpoint of low dielectric constant, the epoxy resin (A) may be a biphenylene skeleton-containing phenol aralkyl type epoxy resin or a dicyclopentadiene-modified phenol type epoxy resin.

The content of the epoxy resin (A) in the resin composition for encapsulating a semiconductor is not particularly limited, but may be 5% by mass or more and 20% by mass or less, and 6% by mass or more and 15% by mass or less. It may be 7% by mass or more and 12% by mass or less.

((B) Phenol resin curing agent)
The (B) phenol resin curing agent used in the present embodiment is not particularly limited. For example, it is a phenol resin curing agent having an action of mainly enhancing moldability and reacts with the epoxy group of the (A) epoxy resin. Examples thereof include a phenol resin curing agent having two or more possible phenolic hydroxyl groups in one molecule.

Specific examples of the (B) phenol resin curing agent include, for example, novolak-type phenol resins such as phenol novolac resin, cresol novolak resin, trisphenol methane-type phenol novolak resin, and naphthol novolak resin; and many such as triphenol methane-type phenol resin. Functional phenolic resin; modified phenolic resin such as terpen-modified phenolic resin, formaldehyde-modified triphenylmethane-type phenolic resin, formaldehyde-modified trihydroxyphenylmethane-type phenolic resin, dicyclopentadiene-modified phenolic resin; phenylene skeleton and / or Examples thereof include a phenol aralkyl resin having a biphenylene skhenol form, a phenylene and / or an aralkyl type phenol resin such as a naphthol aralkyl resin having a biphenylene skeletron, and a biphenyl aralkyl phenol resin; a bisphenol compound such as bisphenol A and bisphenol F; and the like. One of these may be used alone, or two or more thereof may be used in combination.

(B) The phenol resin curing agent may be a novolak type phenol resin, a polyfunctional phenol resin, an aralkyl type phenol resin, an aralkyl type phenol resin, or a phenol aralkyl resin (for example, a biphenylene skeleton-containing phenol). Phenol formaldehyde) or biphenyl phenol formaldehyde may be used.

The content ratio of the (A) epoxy resin to the (B) phenol resin curing agent in the resin composition for encapsulating the semiconductor of the present embodiment is (B) with respect to one epoxy group in the (A) epoxy resin. The number of phenolic hydroxyl groups in the phenol resin curing agent may be 0.5 or more and 1.5 or less, or 0.9 or more and 1.2 or less.
The content ratio of (A) epoxy resin and (B) phenol resin curing agent is selected so that the phenolic hydroxyl groups in (B) phenol resin curing agent are within the above range with respect to the epoxy groups in (A) epoxy resin. By doing so, a molded product of a resin composition for encapsulating a semiconductor having well-balanced performance can be obtained.

((C) Curing accelerator)
The (C) curing accelerator used in the present embodiment is not particularly limited, and examples thereof include a curing accelerator generally used as a curing accelerator for epoxy resins.
Specific examples of the (C) curing accelerator include, for example, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonen-5, 5,6-. Cycloamidine compounds such as dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7; these cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4- Kinone compounds such as naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenol resin Compounds with intramolecular polarization formed by adding a compound having a π bond such as; Tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and derivatives thereof; 2 -Methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-Phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [ 2'-Undecylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine And other imidazole compounds such as diamino-s-silicon-containing triazine compounds having an imidazole ring and derivatives thereof; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine and the like. Organic phosphine compounds; these organic phosphine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3- A phosphorus compound having intramolecular polarization by adding a quinone compound such as dimethoxy-5-methyl-1,4-benzoquinone or phenyl-1,4-benzoquinone, or a compound having a π bond such as diazophenylmethane or phenol resin; Tetrafe Tetra-substituted phosphonium-tetra-substituted borates such as nylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate; 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholin tetraphenyl Tetraphenylborone salts such as borate and derivatives thereof; and the like. One of these may be used alone, or two or more thereof may be used in combination.
From the viewpoint of the fluidity of the resin composition for encapsulating a semiconductor, the (C) curing accelerator may be an imidazole compound.

The content of the (C) curing accelerator is not particularly limited, but is based on 100 parts by mass of the total amount of the (A) epoxy resin, (B) phenol resin curing agent, and (G) benzoxazine resin described later. , 0.2 parts by mass or more and 8.0 parts by mass or less, or 1.0 parts by mass or more and 5.0 parts by mass or less.
When the content of the curing accelerator (C) is within the above range, the curability becomes good and the fluidity of the resin composition for semiconductor encapsulation becomes good.

((D) Inorganic filler)
The inorganic filler (D) is not particularly limited, and examples thereof include known inorganic fillers generally used in resin compositions for encapsulating semiconductors.
Specific examples of the inorganic filler (D) include oxide powders of fused silica, crystalline silica, crushed silica, synthetic silica, alumina, titania, magnesia and the like; hydroxide powders of aluminum hydroxide, magnesium hydroxide and the like. Nitride powders such as silicon nitride, aluminum oxide, boron nitride, etc .; Zircon, calcium silicate, calcium carbonate, potassium titanate, barium titanate, silicon carbide, beryllia, zirconia, fosterite, steatite, spinel, mulite, etc. Other powders; spherical beads; single crystal fibers; glass fibers; and the like. One of these may be used alone, or two or more thereof may be used in combination.
From the viewpoint of reducing the coefficient of thermal expansion, the inorganic filler (D) may be fused silica, or may be alumina from the viewpoint of enhancing high thermal conductivity.

The shape of the inorganic filler is not particularly limited, but may be spherical from the viewpoint of improving the fluidity during molding and suppressing the wear of the mold.

The average particle size of the inorganic filler (D) is not particularly limited, but may be 0.5 μm or more and 40 μm or less, 1 μm or more and 30 μm or less, or 5 μm or more and 30 μm. Further, the maximum particle size of the (D) inorganic filler may be 105 μm or less.
When the average particle size is 0.5 μm or more, the fluidity of the resin composition can be controlled and the moldability can be improved. Further, when the average particle size is 40 μm or less, it is possible to control the warp of the molded product obtained by curing the resin composition and prevent a decrease in dimensional accuracy. Further, when the maximum particle size is 105 μm or less, the moldability of the resin composition can be improved.

The content of the (D) inorganic filler in the semiconductor encapsulating resin composition may be 60% by mass or more and 90% by mass or less, or 65% by mass or more and 85% by mass or less. When the content of the inorganic filler (D) is within the above range, the moldability and fluidity of the resin composition are improved, and the dimensional accuracy, moisture resistance, and mechanical strength of the molded product are improved.

((E) Resin particles)
The resin particles (E) used in the present embodiment are made of a resin containing a structural unit derived from a predetermined cyclic olefin compound.

<Cyclic olefin compound>
The cyclic olefin compound is a compound represented by the following general formula (1).

In the general formula (1), R ¹ to R ¹² may be the same or different from each other, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. R ⁹ and R ¹⁰ and R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group. R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may be coupled to each other to form a ring. Further, n indicates 0 or a positive integer, and when n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit.
Examples of the hydrocarbon group in R ¹ to R ¹² include an alkyl group having 1 to 10 carbon atoms; and the like, which may be a methyl group or an ethyl group.
Examples of the halogen atom in R ¹ to R ¹² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and may be a fluorine atom and a chlorine atom.
R ¹ to R ¹² may be a hydrogen atom, a methyl group, an ethyl group, or a hydrogen atom.
Examples of the divalent hydrocarbon group formed by integrating R ⁹ and R ¹⁰ or R ¹¹ and R ¹² include an alkylene group having 1 to 10 carbon atoms; and a methylene group and an ethylene group. It may be.
As ^{the ring formed by bonding R 9} or R ¹⁰ and R ¹¹ or R ¹² to each other, the formed ring may be a monocyclic ring, a polycyclic ring, or a polycyclic ring having a crosslink. It may be a ring having a double bond, or it may be a ring composed of a combination of these rings. Further, these rings may have a substituent such as a methyl group.
n may be 1 or 0.

Specific examples of the cyclic olefin compound include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, 5-pentylnorbornene, and the like. Norbornenes; tetracyclododecenes such as tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene; etc. Be done. One of these may be used alone, or two or more thereof may be used in combination.
The cyclic olefin compound may be norbornene or tetracyclododecene from the viewpoint of low dielectric constant.

<Structural unit derived from cyclic olefin compound>
Examples of the structural unit derived from the cyclic olefin compound include structural unit X represented by the following general formula (4); structural unit Y represented by the following general formula (5), and the like.
The structural unit derived from the cyclic olefin compound may be a structural unit represented by the following general formula (5) from the viewpoint of low dielectric constant.

^R 1 ^{~ R 12} and n in the general formula (4), is identical to ^R 1 ^{~ R 12} and n in the general formula (1).
The polymer X containing the structural unit X represented by the general formula (4) is, for example, a known catalyst such as a metal catalyst (Grubbs catalyst), a pyrylium-tetrafluoroborate salt, or the like, using the cyclic olefin compound. It is obtained by a known method such as ring-opening metathesis polymerization using and hydrogenation (hydrogenation).

^R 1 ^{~ R 12} and n in Formula (5) in is the same as ^R 1 ^{~ R 12} and n in the general formula (1).
The polymer Y containing the structural unit Y represented by the general formula (5) is, for example, addition-copolymerized with the cyclic olefin compound and an α-olefin described later using a known catalyst such as a metallocene catalyst. It can be obtained by a known method such as a method.

<Structural units other than structural units derived from cyclic olefin compounds>
Structural units other than the structural unit derived from the cyclic olefin compound include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1 Examples thereof include structural units derived from α-olefins such as nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. One of these may be used alone, or two or more thereof may be used in combination.
The structural unit other than the structural unit derived from the cyclic olefin compound may be a structural unit derived from ethylene from the viewpoint of low dielectric constant.

<(E) Resin constituting resin particles>
The structure of the resin (that is, the resin containing a structural unit derived from a predetermined cyclic olefin compound) constituting the resin particles is, for example, a polymer represented by the following general formula (6) (the above general formula). (A type of polymer X having a structural unit X represented by (4)); a polymer represented by the following general formula (7) (a polymer Y having a structural unit Y represented by the above general formula (5)). ); And so on. One of these may be used alone, or two or more thereof may be used in combination.
(E) The structure of the resin constituting the resin particles is a polymer represented by the following general formula (7) (a polymer having a structural unit Y represented by the above general formula (5)) from the viewpoint of low dielectric constant. It may be a kind of Y).

(In the general formula (6), X ₁ and X ₂ may be the same or different, respectively, and are hydrogen atoms or hydrocarbon groups. P represents a positive integer.)
Examples of the hydrocarbon group of X ₁ and X ₂ include an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms; and may be a methyl group or an ethyl group.
The X ₁ and X ₂ may be a hydrogen atom, a methyl group, an ethyl group, or a hydrogen atom.

(In the general formula (7), Y ₁ and Y ₂ may be the same or different, respectively, and are hydrogen atoms or hydrocarbon groups. Further, q and r represent positive integers, respectively. )
Examples of the hydrocarbon group of Y ₁ and Y ₂ include an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms; and may be a methyl group or an ethyl group.
Examples of Y ₁ and Y ₂ may be a hydrogen atom, a methyl group, an ethyl group, or a hydrogen atom.

(E) When the resin constituting the resin particles is a copolymer, it may be a block copolymer or a random copolymer.

Further, as a commercially available product of the resin constituting the resin particles (E), for example, TOPAS (registered trademark) (manufactured by Polyplastics Co., Ltd., the polymer represented by the above general formula (7) (Y1 and Y2 are all hydrogen). )), Appel (registered trademark) (manufactured by Mitsui Chemicals, Inc., polymer represented by the above general formula (7)), Zeonex (registered trademark) (manufactured by Nippon Zeon Corporation, heavy weight represented by the above general formula (6)). Combined), Zeonoa (registered trademark) (manufactured by Zeon Corporation, polymer represented by the above general formula (6)), and the like.

The average particle size of the resin particles (E) used in the present embodiment is not particularly limited. The average particle size of the resin particles (E) may be 0.1 μm or more and 50 μm or less, and 10 μm or more, from the viewpoint of the fluidity and dispersibility of the resin composition for semiconductor encapsulation and the stability of the dielectric constant. It may be 40 μm or less.
Further, the shape of the resin particles (E) used in the present embodiment is not particularly limited.

The method for producing the resin particles (E) used in the present embodiment is not particularly limited. Examples of the method for producing the resin particles (E) include a method in which the resin particles are extruded into a rod shape in a molten state, cut into an appropriate length with a cutter, and crushed with a crusher having a built-in classifier. The crusher is not particularly limited as long as it can crush to a size of 5 mm or less, for example, a cutting mill, a ball mill, a cyclone mill, a hammer mill, a vibration mill, a cutter mill, a grind mill, and a speed. Mill, etc. The crusher may be a speed mill.
The pulverization by a pulverizer may be performed in two or more steps, for example, the sheet-like composition is pulverized relatively coarsely by a coarse pulverizer or the like, and then further finely pulverized by a fine pulverizer to obtain a pulverized product.

Here, the pulverization may be performed at a low temperature of 10 ° C. or lower or in a frozen atmosphere. The crushing temperature is not particularly limited, but may be 0 ° C. or lower, -50 ° C. or higher and 0 ° C. or lower, -30 ° C. or higher and 0 ° C. or lower, or −20 ° C. or higher. It may be 0 ° C. or lower. By pulverizing in such a low temperature or freezing atmosphere, the resin containing a structural unit derived from a predetermined cyclic olefin compound is low temperature brittle and is easily finely pulverized.
As the cold source, for example, a liquefied nitrogen refrigerator is used. Further, as the cold source, a dry dehumidifier using a rotary rotor (low temperature low dew point air generator) or the like may be used.

Further, the pulverization may be performed by "classification pulverization" in which pulverization of a resin containing a structural unit derived from a predetermined cyclic olefin compound and classification of the pulverized product are performed at the same time. Examples of the device capable of crushing and classifying at the same time include a crusher with a built-in classifier including a crushing unit for crushing the object to be crushed and a classifying unit for classifying the crushed material. The crusher with a built-in classifier is not particularly limited, but for example, it has a ring shape in which a crushing object is put into the device together with a cooling gas, supported by a rotating shaft, and has a crushing blade having a plurality of irregularities on the outer surface. When the crushing object passes between the crushing rotor and the liner that is fixedly arranged, the refrigerating crushing device is configured so that the crushing object is repeatedly crushed between these two members. You may use it. Such a freezing and crushing apparatus is described in, for example, Japanese Patent Application Laid-Open No. 57-60060, Japanese Patent Application Laid-Open No. 2017-912, and the like.

The rotation speed of the crusher with a built-in classifier is not particularly limited, but from the viewpoint of efficiently crushing the object to be crushed, it may be 1000 rpm or more and 8000 rpm or less, 2000 rpm or more and 6000 rpm, or 2000 rpm. It may be more than 5000 rpm or less.
The pulverized product (resin particles) obtained by the pulverization is classified into a desired particle size by sieve classification and air classification.
The mesh size used for the sieve classification may be 10 μm or more and 100 μm or less, 20 μm or more and 60 μm or less, or 30 μm or more and 50 μm or less.

The content of the (E) resin particles in the semiconductor encapsulating resin composition is not particularly limited, but the moldability, fluidity and molding shrinkage (thermal expansion rate) of the semiconductor encapsulating resin composition, and From the viewpoint of low dielectric constant of the molded product, it may be 5% by mass or more and 20% by mass or less, or 5% by mass or more and 15% by mass or less.

The total content of (A) epoxy resin, (B) phenol resin curing agent, (C) curing accelerator, (D) inorganic filler, and (E) resin particles in the resin composition for encapsulating semiconductors is It may be 100% by mass, that is, the resin composition for semiconductor encapsulation is (A) epoxy resin, (B) phenol resin curing agent, (C) curing accelerator, (D) inorganic filler and (E). ) It may consist of only five components of the resin particles.

((F) Low stress material)
The resin composition for semiconductor encapsulation of the present embodiment may further contain (F) a low-stress material from the viewpoint of reducing the molding shrinkage rate (thermal expansion rate).

Examples of the (F) low stress material which is an optional component in the semiconductor encapsulating resin composition of the present embodiment include rubbers such as butadiene rubber, nitrile rubber, silicone rubber, and butadiene / styrene copolymer; epoxy-modified rubber. Kind; Silicone oils; Core shell rubbers; etc., and commercially available products can also be used. One of these may be used alone, or two or more thereof may be used in combination.
The low-stress material (F) may be rubbers, epoxy-modified rubbers, butadiene-styrene copolymer, or epoxy-modified polybutadiene rubber (epoxy equivalent 200 or more and 600 or less).

The content of the (F) low stress material in the resin composition for encapsulating a semiconductor is not particularly limited. The content of the low stress material (F) may be 0.1% by mass or more and 1.5% by mass or less, or 0.1% by mass or more and 1.0% by mass or less. When the content of the low stress material (F) is within the above range, the molding shrinkage rate (thermal expansion rate) can be lowered without impairing the curing characteristics even if the content of the resin particles (E) is large. ..

((G) benzoxazine resin)
The semiconductor encapsulating resin composition of the present embodiment may further contain (G) benzoxazine resin from the viewpoint of low dielectric constant. By further containing the (G) benzoxazine resin in the semiconductor encapsulating resin composition, the content of the (E) resin particles can be reduced.

The (G) benzoxazine resin, which is an optional component in the semiconductor encapsulating resin composition of the present embodiment, is a compound represented by the following general formula (2), and has two or more benzoxazine rings in one molecule. include.

In the general formula (2), X ¹ is an alkylene group having 1 to 10 carbon atoms, a group represented by the following general formula (3), -SO _2- , -CO-, an oxygen atom, or a single bond. Yes, R is a hydrogen atom or a hydrocarbon group having 1 or more and 10 or less carbon atoms, respectively.

In the general formula (3), X ² is a hydrocarbon group having an aromatic ring and having 6 or more and 30 or less carbon atoms, and m is an integer of 0 or 1 or more.

The alkylene group having 1 or more carbon atoms and 10 or less carbon atoms of X ^{1 may be a methylene group or an ethylene group.}
Examples of the hydrocarbon group having 1 to 10 carbon atoms of R include an alkyl group having 1 to 10 carbon atoms; and the like, which may be a methyl group or an ethyl group.
Examples of the hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring of X ^2, for example, a phenylene group, and the like.
X ¹ _is, -SO 2 _-, - _CO-, or -CH ₂ - it was also good, -CH ₂ - may be.
R may be a hydrogen atom.
m may be 0 or 1.

The content of the (G) benzoxazine resin is not particularly limited, but the (A) epoxy resin 100 is in that the resin composition for encapsulating a semiconductor has a low dielectric constant and a low viscosity, and the wire flowability is good. It may be 0 parts by mass or more and 200 parts by mass or less, 20 parts by mass or more and 180 parts by mass or less, or 50 parts by mass or more and 150 parts by mass or less with respect to the mass parts.

By using the resin particles (E) and the benzoxazine resin (G) in combination, a resin composition for encapsulating a semiconductor having excellent wire flowability and molding shrinkage in addition to a low dielectric constant can be obtained.
This is because the content of the (E) resin particles can be reduced while maintaining a low dielectric constant by using the (E) resin particles and the (G) benzoxazine resin in combination, so that the silica content is relatively increased. This is because it is possible to do so.
The total content of the (E) resin particles and the (G) benzoxazine resin in the resin composition for encapsulating a semiconductor is not particularly limited, but is 5% by mass or more from the viewpoint of wire flowability and low molding shrinkage. It may be 30% by mass or less.

The content of the (B) phenol resin curing agent when the (A) epoxy resin and the (G) benzoxazine resin are used in combination is not particularly limited, but has moldability, wire flowability, warpage, or molding shrinkage. From the viewpoint, it may be 1 part by mass or more and 80 parts by mass or less, or 5 parts by mass or more and 60 parts by mass or less with respect to a total of 100 parts by mass of the (A) epoxy resin and (G) benzoxazine resin. good.

The total number of hydroxyl groups (g) generated when the benzoxazine contained in the (G) benzoxazine resin is opened and the phenolic hydroxyl groups (b) in the (B) phenol resin curing agent, and (A) the epoxy resin. The ratio (((b) + (g)) / (a)) (equivalent ratio) to the number of epoxy groups (a) is not particularly limited, but is the same as that of the unreacted component (that is, (A) epoxy resin). Reduce the residual amount of (G) benzoxazine resin and (B) phenol resin curing agent that does not react, or (A) epoxy resin that does not react with (G) benzoxazine resin and (B) phenol resin curing agent). From the viewpoint of reducing the formability or the decrease in the strength of the cured product, it may be 0.5 or more and 1.5 or less, or 1.0 or more and 1.2 or less.
The hydroxyl group (g) generated when the benzoxazine contained in the (G) benzoxazine resin is ring-opened is the amount when all the benzoxazine contained in the (G) benzoxazine resin is ring-opened.

((H) Other components (additives))
In addition to the above components (A) to (G), the semiconductor encapsulating resin composition of the present embodiment contains the semiconductor encapsulating fat composition as long as the effects of the present embodiment are not impaired. (H) Other components (additives) such as flame retardants; coupling agents; mold release agents; colorants; stabilizers such as hydrotalcites; ion scavengers; defoamers; Can be contained as needed. One of these may be used alone, or two or more thereof may be used in combination.

<Flame retardant>
Examples of the flame retardant include compounds containing metal elements such as brominated epoxy resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide and zinc oxide; and phosphorus compounds such as phosphoric acid ester (FP-100). Be done. One of these may be used alone, or two or more thereof may be used in combination.

<Coupling agent>
Examples of the coupling agent include epoxysilane-based coupling agent, aminosilane-based coupling agent, ureidosilane-based coupling agent, vinylsilane-based coupling agent, alkylsilane-based coupling agent, organic titanate-based coupling agent, and aluminum arco. Examples include rate-based coupling agents. One of these may be used alone, or two or more thereof may be used in combination.
The coupling agent may be an aminosilane-based coupling agent from the viewpoint of flame retardancy and curability, and may be γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, It may be γ-aminopropylmethyldiethoxysilane or N-phenyl-3-aminopropyltrimethoxysilane.

<Release agent>
Examples of the release agent include synthetic wax; natural wax such as carnauba wax; higher fatty acid; metal salt of higher fatty acid; and the like. One of these may be used alone, or two or more thereof may be used in combination.

<Colorant>
Examples of the colorant include carbon black, cobalt blue, and the like. One of these may be used alone, or two or more thereof may be used in combination.

<Stabilizer>
Examples of the stabilizer include a solid solution having a hydrotalcite structure such as magnesium, aluminum, hydroxide, carbonate, and hydrate. One of these may be used alone, or two or more thereof may be used in combination.

The total content of (H) and other components (additives) in the semiconductor encapsulant resin composition of the present embodiment is not particularly limited, but may be 0.05% by mass or more and 3% by mass or less. It may be 0.1% by mass or more and 2% by mass or less.

In preparing the resin composition for encapsulating the semiconductor of the present embodiment, for example, (A) epoxy resin, (B) phenol resin curing agent, (C) curing accelerator, and (D) inorganic filler are used. , (E) Resin particles and various other components ((F) low stress material, (G) benzoxazine resin, (H) other components (additives)) contained as needed. Then, the mixture is sufficiently mixed (uniformly dispersed and mixed) using a mixer or the like, heat-kneaded by a kneading device such as a twin-screw extrusion kneader, a thermal roll, or a kneader, and if necessary, cooled and then suitable. It may be crushed to a size.

The resin composition for semiconductor encapsulation of the present embodiment can be used for coating, insulating, encapsulating, and the like of various electric components or various electronic components such as semiconductor elements. Examples of semiconductor elements include transistors, integrated circuits, diodes, thyristors, and the like.
As a method for sealing an electronic component such as a semiconductor element with the semiconductor encapsulating resin composition of the present embodiment, a molding method such as a transfer mold, a compression mold, or an injection mold is used. Molding can be performed, for example, at a temperature of 120 ° C. or higher and 200 ° C. or lower, and a pressure of 2 MPa or higher and 20 MPa or lower. By molding and sealing electronic components such as semiconductor elements under such conditions, resin-sealed electronic component devices and semiconductor devices with excellent reflow resistance and high reliability during high-temperature operation can be obtained. Can be done.

[Semiconductor device]
The semiconductor device of the present embodiment is formed by sealing a semiconductor element with the above-mentioned resin composition for sealing a semiconductor. Specifically, active elements such as semiconductor chips, transistors, diodes, and thyristers, and passive elements such as capacitors, resistors, and coils are mounted on support members such as lead frames, tape carriers, wiring boards, and silicon wafers. However, a semiconductor device in which a necessary portion is sealed with the semiconductor encapsulating resin composition of the present embodiment can be mentioned.

Next, the present disclosure will be specifically described with reference to Examples, but the present disclosure is not limited to these examples.

(Examples 1 to 9 and Comparative Examples 1 and 2)
Each component of the type and content (part by mass) shown in Table 1 is heat-kneaded using a biaxial extrusion kneader under the conditions of a kneading temperature of 100 ° C. and a kneading time of 5 minutes to prepare a resin composition for semiconductor encapsulation. Was prepared. In Table 1, the blank part (“-” in Table 1) indicates that there is no compounding.

Details of each component shown in Table 1 used for preparing the resin composition for semiconductor encapsulation are as follows.

<(A) Epoxy resin>
(A1) Dicyclopentadiene type epoxy resin (trade name: HP-7200, manufactured by DIC Corporation)
(A2) Biphenylene skeleton-containing phenol aralkyl type epoxy resin (trade name: NC-3000, manufactured by Nippon Kayaku Co., Ltd.)

<(B) Phenol resin curing agent>
(B1) Phenolic aralkyl resin containing biphenylene skeleton (trade name: MEHC-7851-SS, manufactured by Meiwa Kasei Co., Ltd.)

<(C) Curing accelerator>
(C1) Imidazole compound (trade name: 2MZA, manufactured by Shikoku Chemicals Corporation)

<(D) Inorganic filler>
(D1) Fused silica (trade name: FB-105FC, manufactured by Denka Co., Ltd., average particle size 11 μm)
(D2) Fused silica (trade name: SC-4500SQ, manufactured by Admatex Co., Ltd., average particle size 1 μm)

<(E) Resin particles>
・ (E1) Cycloolefin copolymer (trade name: TOPAS, manufactured by Polyplastics Co., Ltd.) was put into a crusher with a built-in classifier (trade name: Linlex Mill LX, manufactured by Hosokawa Micron Co., Ltd.) at a temperature of -10 ° C. , Grinding disc 3000 rpm, classification rotor 2300 rpm, supply amount 100 kg / hour, crushing, sieving with 350 mesh (sieving opening: 38 μm or more and 45 μm or less), and “TOPAS crushed product” with an average particle size of 30 μm. Obtained.
(E2) Fluororesin powder as other resin particles (trade name: EA-2000 PW10, manufactured by AGC Inc .; average particle size 2 μm)

<(F) Low stress material>
-(F1) Butadiene-Styrene copolymer (trade name: RICON657, manufactured by Clay Valley)

<(G) Benzoxazine resin>
(G1): Pd-type polybenzoxazine resin (in the general formula (2), X is a methylene group and two Rs are both hydrogen atoms, a benzoxazine resin) (manufactured by Shikoku Kasei Kogyo Co., Ltd.)

<(H) Other ingredients>
・ (H1) Silane coupling agent (trade name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) ・ (H2) Coloring agent (carbon black) (trade name: MA-100RMJ, manufactured by Mitsubishi Chemical Corporation)
・ (H3) Flame retardant (trade name: FP-100, manufactured by Fushimi Pharmaceutical Co., Ltd.)
・ (H4) Release agent (carnauba wax) (Product name: carnauba wax No. 1, manufactured by Toyo Adre Co., Ltd.)
・ (H5) Stabilizer (trade name: ALCAMIZER1, manufactured by Kyowa Chemical Industry Co., Ltd.)

The characteristics of the resin compositions for semiconductor encapsulation prepared in Examples 1 to 9 and Comparative Examples 1 and 2 were measured and evaluated under the measurement conditions shown below. The evaluation results are shown in Table 1.

[Evaluation item]
(1) Spiral flow The spiral flow was measured by transfer molding the obtained resin composition for semiconductor encapsulation at a molding temperature of 175 ° C. and a molding pressure of 9.8 MPa using a mold conforming to the EMMI standard. ..
(2) Relative Pertivity and Dissipation Factor The obtained resin composition for semiconductor encapsulation is transfer-molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 8.0 MPa, and a molding time of 2 minutes to have a diameter of 100 mm and a thickness of 100 mm. A molded product of a 3 mm disk was prepared, and further cured at 175 ° C. for 8 hours to obtain a test piece. The obtained test piece was measured for relative permittivity and dielectric loss tangent at a frequency of 100 MHz according to a general thermocurable plastic test method (JIS K6911-1995 5.14 dielectric constant and dielectric loss tangent).
-Measuring instrument: Impedance measuring device (manufactured by Hewlett-Packard Japan Co., Ltd .: 4291B RF impedance / material analyzer)
・ Measurement frequency: 100MHz
(3) Molding Shrinkage Rate by Molding and Post-Curing The molding shrinkage rate was measured according to a general test method for thermosetting plastics (JIS K6911-1995 5.7 molding shrinkage rate and heat shrinkage rate (molding material)).
The obtained resin composition for encapsulating a semiconductor is transfer-molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 8.0 MPa, and a curing time of 2 minutes, and a test piece for measuring the molding shrinkage rate (annular band outer diameter φ80 mm). Got The dimensions of the outer diameter of the annular band at 4 points (2 points each on the front and back sides) of the test piece for measuring the molding shrinkage were measured. The molding shrinkage rate (%) was calculated by the following formula and used as the molding shrinkage rate (molding shrinkage rate As) by molding.
Further, the test piece for measuring the molding shrinkage rate (molding shrinkage rate As) was post-cured at 175 ° C. for 8 hours, and then the molding shrinkage rate (%) was calculated by the following formula to obtain the molding shrinkage rate (%) by post-curing. Molding shrinkage rate PMC).
Molding shrinkage rate (%) = ((D _1- d ₁ ) / D ₁ + (D _2- d ₂ ) / D ₂ + (D _3- d ₃ ) / D ₃ + (D _4- d ₄ ) / D ₄ ) / 4 * 100
Here, d ₁ to ₄ : The outer diameter (mm) of the test piece annular band measured along each measurement line.
D ₁ to ₄ : Outer diameter (mm) of the groove of the mold corresponding to _{d 1} to ₄ measured at room temperature of 20 ± 2 ° C.
(4) Using the obtained warped resin composition for encapsulating a semiconductor, transfer molding (175 ° C., 120 seconds, 6 MPa) to a thickness of 0.6 mm on a FR4 substrate having a thickness of 54 mm × 55 mm × 0.2 mm (thickness). After molding and post-curing (175 ° C. x 8 hours), warpage was measured at room temperature with a shadow moire device (product name: THERMORE PS200, manufactured by AKROMETRIX) with the resin surface facing up. rice field.
(5) Wire flow rate (wire deformation)
Using the obtained resin composition for encapsulating a semiconductor, an FBGA package (50 mm × 50 mm × 0.54 mm, under the conditions of a mold temperature of 175 ° C. and a curing time of 2 minutes, then a mold temperature of 175 ° C. and a curing time of 8 hours, After molding the chip thickness (0.31 mm) by the transfer molding method, observe the wire deformation with an X-ray inspection device (SMX-1000 Plus, manufactured by Shimadzu Corporation), and observe the wire flow rate (sealing) of the maximum deformed part. The ratio (%) of the maximum distance between the position of the front wire and the position of the wire after sealing with respect to the wire length was measured.
(6) Reflow resistance Obtained after molding an FBGA package (50 mm × 50 mm × 0.54 mm, chip thickness 0.31 mm) by a transfer molding method using the obtained resin composition for encapsulating a semiconductor. The molded product was after-cured at 175 ° C. for 8 hours, and then subjected to a moisture absorption treatment at 30 ° C., a relative humidity of 60% RH, and for 192 hours. After that, it is heated in an infrared reflow furnace at 260 ° C., and after cooling, the interface between the cured resin and the frame and the resin curing are performed by an ultrasonic flaw detector (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., trade name: FS300II). The presence or absence of peeling at the interface between the object and the semiconductor chip was examined, and the number of peelings (NG number) was counted.

From Table 1, for semiconductor encapsulation of Examples 1 to 9 containing (A) epoxy resin, (B) phenol resin curing agent, (C) curing accelerator, (D) inorganic filler, and (E) resin particles. The resin composition (relative permittivity: 3.2 or more and 3.6 or less) is the resin composition for semiconductor encapsulation (relative permittivity: 3.7 or more and 3) of Comparative Examples 1 and 2 containing (E) resin particles. It was found that the relative permittivity could be sufficiently reduced as compared with (0.9 or less).
Further, the resin composition for encapsulating a semiconductor of Example 1 containing resin particles containing a structural unit derived from (E) a cyclic olefin compound (molding shrinkage rate As: 0.33%, molding shrinkage rate PMC: 0.24). %) Is compared with the resin composition for semiconductor encapsulation (molding shrinkage rate As: 0.44%, molding shrinkage rate PMC: 0.52%) of Comparative Example 3 containing other resin particles (fluororesin powder). It was found that the molding shrinkage rate became smaller.
Further, from Table 1, the resin composition for semiconductor encapsulation (molding shrinkage rate As: 0.41%, molding shrinkage rate PMC: 0.37%) of Example 3 further containing (F) low stress material is (F). F) The molding shrinkage rate is lower than that of the resin composition for semiconductor encapsulation of Example 2 which does not contain a low stress material (molding shrinkage rate As: 0.52%, molding shrinkage rate PMC: 0.46%). It turned out that it could be made to.
Further, from Table 1, by comparing Example 9 further containing (G) benzoxazine resin with Example 8 not containing (G) benzoxazine resin, by further containing (G) benzoxazine resin, It was found that the content of the resin particles (E) can be reduced while maintaining a low dielectric constant.

Claims (12)

1. Contains (A) epoxy resin, (B) phenol resin curing agent, (C) curing accelerator, (D) inorganic filler, and (E) resin particles.
   The resin particles (E) are a resin composition for encapsulating a semiconductor, which comprises a resin containing a structural unit derived from a cyclic olefin compound represented by the following general formula (1).
   

   

   
   (In the general formula (1), R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and are R ⁹ and R. ¹⁰ , R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² are bonded to each other to form a ring. Further, n represents 0 or a positive integer, and when n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit.)
2. The semiconductor encapsulating resin composition according to claim 1, wherein the content of the (E) resin particles in the semiconductor encapsulating resin composition is 5% by mass or more and 20% by mass or less.
3. The resin composition for semiconductor encapsulation according to claim 1 or 2, wherein the average particle size of the resin particles (E) is 0.1 μm or more and 50 μm or less.
4. The semiconductor encapsulation according to any one of claims 1 to 3, wherein the resin particles (E) are particles obtained by classifying and pulverizing a resin containing a structural unit derived from the cyclic olefin compound at 10 ° C. or lower. Resin composition.
5. The semiconductor encapsulating resin composition according to any one of claims 1 to 4, wherein the content of the epoxy resin (A) in the semiconductor encapsulating resin composition is 5% by mass or more and 20% by mass or less. thing.
6. The semiconductor encapsulating resin according to any one of claims 1 to 5, wherein the content of the inorganic filler (D) in the semiconductor encapsulating resin composition is 60% by mass or more and 90% by mass or less. Composition.
7. (F) The resin composition for semiconductor encapsulation according to any one of claims 1 to 6, further comprising a low stress material.
8. The semiconductor according to any one of claims 1 to 7, wherein the content of the low stress material (F) in the resin composition for encapsulating a semiconductor is 0.1% by mass or more and 1.5% by mass or less. Resin composition for sealing.
9. (G) Further containing a benzoxazine resin,
   The resin composition for semiconductor encapsulation according to any one of claims 1 to 8, wherein the (G) benzoxazine resin is a compound represented by the following general formula (2).
   

   

   
   (In the general formula (2), X ¹ is an alkylene group having 1 to 10 carbon atoms, a group represented by the following general formula (3), -SO _2- , -CO-, an oxygen atom, or a single bond. R is a hydrogen atom or a hydrocarbon group having 1 or more and 10 or less carbon atoms, respectively.)
   

   

   
   (In the general formula (3), X ² is a hydrocarbon group having an aromatic ring and having 6 or more and 30 or less carbon atoms, and m is an integer of 0 or 1 or more.)
10. The resin composition for encapsulating a semiconductor according to claim 9, wherein the content of the (G) benzoxazine resin is 0 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the (A) epoxy resin.
11. The semiconductor according to claim 9 or 10, wherein the total content of the (E) resin particles and the (G) benzoxazine resin in the semiconductor encapsulating resin composition is 5% by mass or more and 30% by mass or less. Resin composition for sealing.
12. A semiconductor device for encapsulating a semiconductor element using the resin composition for encapsulating a semiconductor according to any one of claims 1 to 11.