JP6221382B2 - Epoxy resin composition and electronic component device - Google Patents

Description

  The present invention relates to an epoxy resin composition and an electronic component device.

  Conventionally, epoxy resins have been widely used in the fields of molding materials, laminates and adhesives. In these fields, since rapid curability is required from the viewpoint of improving productivity, a compound that accelerates the curing reaction, that is, a curing accelerator is generally used in the epoxy resin composition. In addition, epoxy resin-based compositions are also widely used in the field of sealing technology relating to elements of electronic components such as transistors and ICs (Integrated Circuits). This is because epoxy resins are balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. In particular, a combination of an ortho-cresol novolac type epoxy resin and a phenol novolac curing agent has an excellent balance in the above-mentioned characteristics, and thus has become the mainstream as a base resin for molding materials for IC sealing. In such an epoxy resin composition, a nitrogen-containing compound such as tertiary amine, quaternary ammonium, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), imidazole; And phosphorus compounds such as phosphonium salts are used as curing accelerators.

  However, when these curing accelerators are used, the storage stability of the epoxy resin composition is low, and it is necessary to store and transport the resin composition at a low temperature, which causes high costs. From such a problem, development of a curing accelerator having excellent storage stability is desired.

  In order to improve the storage stability of the epoxy resin composition, chemical methods using tetra-substituted phosphonium tetra-substituted borates (for example, see Patent Documents 1 to 3) and the like, and microencapsulation (for example, see Patent Documents 4 and 5) Latentization using physical methods such as these has been proposed.

  In addition, in order to improve solder heat resistance and moisture resistance reliability, an epoxy resin composition using a low molecular weight epoxy resin, a phenol novolac resin, and triphenylphosphine as a curing accelerator has been developed (see, for example, Patent Document 6). .

JP-A 49-118798 JP-A-9-328535 JP-A-11-5829 JP-A-8-337633 JP-A-9-77959 Japanese Patent Publication No. 7-78108

  The chemical method using the above tetra-substituted phosphonium tetra-substituted borate and the physical method such as microencapsulation improve the storage stability of the epoxy resin composition, but satisfy both the storage stability and the fast curability. It was not a thing. In particular, in the case of the microencapsulation technique, the microcapsule may be broken in the production process of the epoxy resin composition, and may not show any potential. On the other hand, when the microcapsules are made strong enough not to be broken in the manufacturing process, the microcapsules are broken slowly in the curing reaction, which causes a problem in rapid curing. From such a situation, from the viewpoint of giving priority to fast curing, which is important for practical use, after using a microencapsulated curing accelerator, store and transport the epoxy resin composition at a low temperature so as not to break the microcapsule. The current situation is going on. Moreover, it was difficult for the epoxy resin composition of Patent Document 6 to exhibit good storage stability.

As described above, the conventional curing accelerators cannot solve the storage stability of the epoxy resin composition, and the development of a curing accelerator that improves the storage stability is desired.
Therefore, this invention makes it a subject to provide an electronic component apparatus provided with the element sealed with the epoxy resin composition excellent in storage stability, and the said epoxy resin composition.

  As a result of intensive studies to solve the above problems, it was found that an epoxy resin composition excellent in storage stability can be obtained by using a phosphine having a hydroxy group in the molecule as a curing accelerator, and the present invention It came to be completed. The present invention is as follows.

<1> (A) An epoxy resin having two or more epoxy groups in one molecule, (B) a phenol resin having two or more phenolic hydroxyl groups in one molecule, and (C) the following general formula (I The epoxy resin composition containing the hardening accelerator containing the phosphine compound shown by this, and (D) inorganic filler.

In formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and m represents an integer of 1 to 3. .

<2> (A) The epoxy resin is biphenylene type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, salicylaldehyde type epoxy resin, naphthols and phenols The epoxy resin composition according to <1>, comprising at least one epoxy resin selected from the group consisting of a copolymerization type epoxy resin, an aralkyl type epoxy resin, a diphenylmethane type epoxy resin, and a triphenylmethane type epoxy resin.

<3> (B) The phenol resin is a biphenylene type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a copolymer type resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and a triphenylmethane type phenol resin. The epoxy resin composition according to <1> or <2>, comprising at least one phenol resin selected from the group consisting of:

<4> (A) The epoxy resin includes a biphenyl type epoxy resin, and (B) the phenol resin includes a biphenylene type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a benzaldehyde type phenol resin, and an aralkyl type phenol resin. The epoxy resin composition according to <1>, further comprising at least one phenol resin selected from the group consisting of a copolymer resin, and a triphenylmethane type phenol resin and a novolac type phenol resin.

The electronic component apparatus which has a <5> element and the hardened | cured material of the epoxy resin composition of any one of said <1>-<4> which seals the said element.

  ADVANTAGE OF THE INVENTION According to this invention, an electronic component apparatus provided with the epoxy resin composition excellent in storage stability and the element sealed with this epoxy resin composition can be provided.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, in the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.
Hereinafter, the present invention will be described in detail.

<Epoxy resin composition>
The epoxy resin composition of the present invention comprises (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a phenol resin having two or more phenolic hydroxyl groups in one molecule, and (C ) A curing accelerator containing a phosphine compound represented by the following general formula (I), and (D) an inorganic filler.

In formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and m represents an integer of 1 to 3. .

The reason why the epoxy resin composition is excellent in storage stability by containing a phosphine having a hydroxy group in the molecule as a curing accelerator can be considered as follows.
When the hydroxy group is not separated and becomes an ion, the hydroxy group is said to show a strong inducing effect. This inductive effect reduces the nucleophilicity of the phosphorus atom and makes it difficult for the curing reaction to proceed. Thus, it is considered that good storage stability is exhibited.

[(A) Epoxy resin]
(A) An epoxy resin contains the epoxy resin which has a 2 or more epoxy group in 1 molecule. Examples of epoxy resins having two or more epoxy groups in one molecule include biphenylene type epoxy resins, stilbene type epoxy resins, sulfur atom-containing epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, and salicylaldehyde type epoxy resins. And at least one selected from the group consisting of copolymerized epoxy resins of naphthols and phenols, aralkyl-type epoxy resins, diphenylmethane-type epoxy resins, and triphenylmethane-type epoxy resins. The epoxy resin mentioned here is also called a specific epoxy resin. A specific epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  (A) The epoxy resin may contain other epoxy resins other than the specific epoxy resin. Examples of other epoxy resins include epoxy resins that are usually used in the field, and examples include biphenyl type epoxy resins.

  (A) When using a specific epoxy resin as an epoxy resin, the total content of the specific epoxy resin in the total amount of the epoxy resin is preferably 60% by mass or more from the viewpoint of exhibiting the respective performances of the specific epoxy resin. It is more preferably 75% by mass or more, and further preferably 90% by mass or more.

  The epoxy equivalent of the epoxy resin is preferably 90 g / eq to 500 g / eq, more preferably 140 g / eq to 450 g / eq, and still more preferably 190 g / eq to 400 g / eq.

  The melting point or softening point of the epoxy resin is preferably 50 ° C to 240 ° C, more preferably 65 ° C to 220 ° C, and still more preferably 80 ° C to 200 ° C.

[(B) Phenolic resin]
As the curing agent, (B) a phenol resin having two or more phenolic hydroxyl groups in one molecule is used. As such a phenol resin, a group consisting of a biphenylene type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a copolymer resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and a triphenylmethane type phenol resin. The at least 1 sort selected from more is mentioned. The phenol resin mentioned here is also called a specific phenol resin. A specific phenol resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  (B) The phenol resin may contain other phenol resins other than the specific phenol resin. Examples of other phenolic resins include phenolic resins that are usually used in the field.

  (B) When using a specific phenol resin as the phenol resin, the total content of the specific phenol resin in the total amount of the phenol resin is preferably 60% by mass or more, from the viewpoint of exhibiting the performance of each specific phenol resin. It is more preferably 75% by mass or more, and further preferably 90% by mass or more.

  The hydroxyl equivalent of the phenol resin is preferably 70 g / eq to 300 g / eq, more preferably 120 g / eq to 250 g / eq, and still more preferably 170 g / eq to 200 g / eq.

  The melting point or softening point of the phenol resin is preferably 50 ° C to 130 ° C, more preferably 60 ° C to 110 ° C, and still more preferably 70 ° C to 90 ° C.

  The content ratio of (A) epoxy resin and (B) phenol resin is set so that the ratio of hydroxyl equivalent of phenol resin to epoxy equivalent of epoxy resin (hydroxyl equivalent / epoxy equivalent) is in the range of 0.5-2. Preferably, it is 0.7-1.5, More preferably, it is 0.8-1.3. When the ratio is 0.5 or more, the epoxy resin is sufficiently cured and the cured product tends to have excellent heat resistance, moisture resistance, and electrical characteristics. Moreover, when the ratio is 2 or less, the amount of phenolic hydroxyl groups remaining in the cured resin is suppressed, and the electrical characteristics and moisture resistance tend to be excellent.

The following is mentioned as an example of the combination of (A) epoxy resin and (B) phenol resin.
(A) The epoxy resin is a biphenylene type epoxy resin, a stilbene type epoxy resin, a sulfur atom-containing epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a salicylaldehyde type epoxy resin, a copolymer of naphthols and phenols Type epoxy resin, aralkyl type epoxy resin, diphenylmethane type epoxy resin and at least one epoxy resin selected from the group consisting of triphenylmethane type epoxy resin, (B) phenol resin is biphenylene type phenol resin, aralkyl type A small amount selected from the group consisting of phenolic resins, dicyclopentadiene type phenolic resins, benzaldehyde type phenolic resins and aralkyl type phenolic resins, and triphenylmethane type phenolic resins. Both containing one phenolic resin.
(A) The epoxy resin contains a biphenyl type epoxy resin, and (B) the phenol resin is a biphenylene type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a benzaldehyde type phenol resin and an aralkyl type phenol resin. It contains at least one phenol resin selected from the group consisting of a polymerization type resin, a triphenylmethane type phenol resin and a novolac type phenol resin.

[(C) Curing accelerator]
(C) A hardening accelerator contains the phosphine compound shown by the following general formula (I).

In formula (I), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m represents an integer of 1 to 3.

Formula (I) the number of carbon atoms in the alkyl group represented by ^{R 1} and ^{R 2} in the 1 to 12, preferably 1 to 10, more preferably 1 to 8, 1 to 6 is more preferable.
R ¹ and carbon atoms in the alkoxy group represented by ^{R 2} is 1 to 12, preferably 1 to 10, more preferably 1 to 8, 1 to 6 is more preferable.

In addition, the alkyl group and alkoxy group represented by R ¹ and R ² in Formula (I) may be linear, branched or cyclic.

The alkyl group and alkoxy group represented by R ¹ and R ² in Formula (I) may have a substituent. Examples of the substituent include an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, and a halogen atom. The alkyl group and alkoxy group represented by R ¹ and R ² are preferably unsubstituted.

R ¹ and R ² in formula (I) are preferably hydrogen atoms.

  In the formula (I), m represents an integer of 1 to 3, and m is preferably 2 or 3, and more preferably 3 from the viewpoint of storage stability.

  As the curing accelerator, in addition to the phosphine compound represented by the general formula (I), other conventionally known curing accelerators may be used in combination. As other curing accelerators, those usually used in the art can be appropriately selected and used. The content of the phosphine compound represented by the general formula (I) in the total curing accelerator is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass. Further preferred.

[(D) Inorganic filler]
The epoxy resin composition contains (D) an inorganic filler. By containing the inorganic filler, it is possible to improve the thermal linear expansion coefficient, thermal conductivity, elastic modulus and the like of the cured product.

  As the inorganic filler, those generally used for sealing molding materials can be appropriately selected and used, and are not particularly limited. For example, inorganic fillers include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Examples include particles of spinel, mullite, titania, talc, clay, mica, etc .; beads formed by spheroidizing them.

  Moreover, you may use the inorganic filler which has a flame-retardant effect. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as composite hydroxide of magnesium and zinc, and particles such as zinc borate. Among these, fused silica particles are preferable from the viewpoint of reducing the linear expansion coefficient, and alumina particles are preferable from the viewpoint of high thermal conductivity. These inorganic fillers may be used alone or in combination of two or more.

  The content of the inorganic filler is not particularly limited as long as the effect of the present invention can be obtained, and is preferably in the range of 55 volume% to 90 volume% with respect to the total amount of the epoxy resin composition. If the content of the inorganic filler is 55% by volume or more, the cured product tends to be excellent in the thermal linear expansion coefficient, thermal conductivity, elastic modulus, and the like, and if it is 90% by volume or less, the viscosity of the epoxy resin composition The rise is suppressed, the fluidity is excellent, and the package tends to be easily molded.

  The average particle diameter of the inorganic filler is preferably 1 μm to 50 μm, and more preferably 10 μm to 30 μm. When the average particle size of the inorganic filler is 1 μm or more, an increase in the viscosity of the epoxy resin composition is easily suppressed, and when it is 50 μm or less, the mixing property between the epoxy resin composition and the inorganic filler is improved and cured. The package obtained by the above tends to be uniform, variation in characteristics is suppressed, and the filling property to a narrow region tends to be improved.

  From the viewpoint of fluidity, the particle shape of the inorganic filler is preferably spherical rather than rectangular, and the particle size distribution of the inorganic filler is preferably distributed over a wide range. For example, when the inorganic filler is contained in an amount of 75% by volume or more, 70% by mass or more of the particles are spherical particles, and the particle size of the spherical particles is preferably distributed in a wide range of 0.1 μm to 80 μm. Since such an inorganic filler is easy to form a close-packed structure, even if the content of the inorganic filler is increased, there is little increase in viscosity of the epoxy resin composition, and an epoxy resin composition excellent in fluidity can be obtained. Can do.

[Anion exchanger]
The epoxy resin composition may contain an anion exchanger as necessary. In particular, when an epoxy resin composition is used as a molding material for sealing, an anion exchanger may be contained from the viewpoint of improving moisture resistance and high temperature storage characteristics of an electronic component device including an element to be sealed. preferable.

  There is no restriction | limiting in particular as an anion exchanger, The thing generally used in the said technical field conventionally is mentioned. Examples of the anion exchanger include hydrosartite compounds represented by the following formula (II); hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth; An anion exchanger can be used individually by 1 type or in combination of 2 or more types.

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (II)
(0 <X ≦ 0.5, m is a positive number)

Hydrosartite compounds are captured by substituting anions such as halogen ions with CO ₃ in the structure, and halogen ions incorporated into the crystal structure are desorbed at about 350 ° C. or higher until the crystal structure is destroyed. It has no properties. Examples of hydrosartite having such properties include Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O produced as a natural product, and Mg _4.3 Al ₂ (OH) _12.6 as a synthetic product. CO ₃ · mH ₂ O and the like can be mentioned. Moreover, the epoxy resin composition of this invention shows the acidity of pH 3-5 and the extract of the hardened | cured material which uses the pure by the influence of the phenol resin of (B) component. Therefore, the epoxy resin composition of the present invention is an environment that easily corrodes aluminum, which is an amphoteric metal, but the hydrosartite compound also has an action of adsorbing an acid, so that the extract is brought close to neutrality. There is also. It can be inferred that corrosion of aluminum can be effectively prevented by the action effect of the addition of the hydrosartite compound.

In addition, hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth and antimony can also be captured by replacing halogen ions with hydroxide ions, and these ion exchanges. The body shows excellent ion exchange capacity on the acidic side. Regarding the epoxy resin composition of the present invention, since the extract is on the acidic side as described above, these hydrated oxides are also particularly effective for preventing corrosion of aluminum. Examples of such hydrous oxides are MgO _n · H ₂ O, Al ₂ O ₃ · nH ₂ O, ZrO ₂ · H ₂ O, Bi ₂ O ₃ · H ₂ O, Sb ₂ O ₅ · nH _2. Hydrous oxides such as O are mentioned.

  The content of the anion exchanger is not particularly limited as long as it is a sufficient amount that can capture anions such as halogen ions. When the epoxy resin composition contains an anion exchanger, the content of the anion exchanger relative to the epoxy resin (A) is preferably 0.1% by mass to 30% by mass, and 1% by mass to 5% by mass. % Is more preferable.

[Release agent]
The epoxy resin composition may contain a release agent from the viewpoint of exhibiting good release properties for the mold in the molding step. The kind in particular of a mold release agent is not restrict | limited, A mold release agent well-known in the said technical field is mentioned. Specific examples of the release agent include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. Can be mentioned. A mold release agent may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, as the release agent, an oxidized or non-oxidized polyolefin wax is preferable.

  Examples of polyolefin waxes include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as H4, PE, and PED series manufactured by Hoechst.

When the epoxy resin composition contains a polyolefin wax as a release agent, the content of the polyolefin wax is preferably 0.01% by mass to 10% by mass with respect to (A) the epoxy resin, and 0.1% by mass. % To 5% by mass is more preferable. If the content of the polyolefin wax is 0.01% by mass or more, the release property tends to be sufficient, and if it is 10% by mass or less, the adhesiveness tends to be sufficient.
Moreover, when using other mold release agent together with polyolefin-type wax, 0.1 mass%-10 mass% are preferable with respect to (A) epoxy resin, and 0.5 mass is preferable. % To 3% by mass is more preferable.

[Flame retardants]
The epoxy resin composition may contain a flame retardant as necessary in order to impart flame retardancy. The type of flame retardant is not particularly limited. Specifically, examples of the flame retardant include known organic compounds or inorganic compounds containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom, a metal hydroxide, and acenaphthylene. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type.
The content of the flame retardant is not particularly limited as long as the flame retardant effect is achieved. When the epoxy resin composition contains a flame retardant, the content of the flame retardant is preferably 1% by mass to 30% by mass and more preferably 2% by mass to 15% by mass with respect to (A) the epoxy resin.

[Coupling agent]
The epoxy resin composition may contain a coupling agent as necessary from the viewpoint of enhancing the adhesion between the resin component and the inorganic filler. The type of coupling agent is not particularly limited. As the coupling agent, known coupling agents such as various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, titanium compound, aluminum chelate compound, aluminum and zirconium-containing compound may be mentioned. These coupling agents may be used alone or in combination of two or more.

  When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably 0.05% by mass to 5% by mass with respect to (D) the inorganic filler, and 0.1% by mass. -2.5 mass% is more preferable. If it is 0.05% by mass or more, the adhesion to the frame tends to be improved, and if it is 5% by mass or less, the moldability of the package tends to be excellent.

[Stress relaxation agent]
The epoxy resin composition may contain a stress relaxation agent such as silicone oil and silicone rubber particles as necessary. By containing a stress relaxation agent, it is possible to reduce the amount of warpage deformation and package cracks of the package. As a usable stress relaxation agent, a known flexible agent (stress relaxation agent) generally used in the technical field can be appropriately selected and used.

  In general, the flexible agents used are thermoplastic elastomers such as silicone, polystyrene, polyolefin, polyurethane, polyester, polyether, polyamide, polybutadiene, NR (natural rubber), NBR (acrylonitrile-butadiene rubber), and acrylic rubber. Rubber particles such as urethane rubber and silicone powder; Core-shell structures such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer And the like. A stress relaxation agent may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, silicone-based flexible agents are preferable, and examples of the silicone-based flexible agents include those having an epoxy group, those having an amino group, and those obtained by modifying these with a polyether.

[Colorants, etc.]
The epoxy resin composition may contain a colorant such as carbon black, organic dye, organic pigment, titanium oxide, red lead, bengara and the like. In addition, you may contain various additives in the range which does not reduce the effect by this invention as needed.

[Preparation of epoxy resin composition]
Any method may be used for preparing the epoxy resin composition as long as various components can be uniformly dispersed and mixed. As a general technique, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized. More specifically, the epoxy resin composition is, for example, mixed and stirred with a predetermined amount of the above-described components, and kneaded with a kneader, roll, extruder, or the like that has been heated to 70 ° C. to 140 ° C. in advance, It can be obtained by a method such as cooling and grinding. The epoxy resin composition is easy to handle when it is tableted with a size and mass that meet the molding conditions of the package.

[Electronic component equipment]
The electronic component device of the present invention includes an element and a cured product of the epoxy resin composition that seals the element. Examples of the electronic component device include a device in which an element such as an active element or a passive element is mounted on a support member, and the element is sealed with the epoxy resin composition of the present invention. Examples of the support member include a lead frame, a wired tape carrier, a wiring board, glass, and a silicon wafer. Examples of the active element include a semiconductor chip, a transistor, a diode, and a thyristor. Examples of the passive element include a capacitor, a resistor, and a coil.

  More specifically, for example, after fixing a semiconductor element on a lead frame and connecting a terminal part of an element such as a bonding pad and a lead part by wire bonding or bump, the epoxy resin composition of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin) Small outline package (TFP), general resin-encapsulated ICs such as TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) in which a semiconductor chip connected to a tape carrier with bumps is encapsulated with the epoxy resin composition of the present invention ); Semiconductor chip connected to wiring formed on wiring board or glass by wire bonding, flip chip bonding, solder, etc. COB (Chip On Board) modules, hybrid ICs, multi-devices in which active elements such as capacitors, transistors, diodes, and thyristors and / or passive elements such as capacitors, resistors, and coils are sealed with the epoxy resin composition of the present invention. Chip module: An element is mounted on the surface of an organic substrate on which a wiring board connection terminal is formed on the back surface, and the element and the wiring formed on the organic substrate are connected by bump or wire bonding, and then the epoxy resin composition of the present invention Examples include BGA (Ball Grid Array) and CSP (Chip Size Package) in which the elements are sealed. The epoxy resin composition of the present invention can also be used effectively for printed circuit boards.

  A method for sealing an electronic component device using the epoxy resin composition of the present invention is not particularly limited, and methods known in the art can be applied. For example, although a low pressure transfer molding method is common, an injection molding method, a compression molding method, or the like may be used.

  The epoxy resin composition of the present invention is excellent in storage stability. Using such an epoxy resin composition, it becomes possible to provide electronic component devices such as IC and LSI, and their industrial value is high.

  EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.

[Example 1]
The various components shown below were blended in parts by mass shown in Table 1, and roll kneading was performed under conditions of a kneading temperature of 80 ° C. and a kneading time of 15 minutes, whereby Examples 1 to 7 and Comparative Examples 1 to 5 respectively. An epoxy resin composition was obtained.

(Preparation of epoxy resin composition)
The following were prepared as epoxy resins.
Epoxy resin 1: biphenyl type epoxy resin having an epoxy equivalent of 196 g / eq and a melting point of 106 ° C. (trade name YX-4000H, manufactured by Japan Epoxy Resin Co., Ltd.)
Epoxy resin 2: epoxy resin 192 g / eq, melting point 79 ° C. diphenylmethane type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name YSLV-80XY)
Brominated epoxy resin: Brominated bisphenol A type epoxy resin having an epoxy equivalent of 393 g / eq, a softening point of 80 ° C., and a bromine content of 48 mass% as an epoxy resin having a flame-retardant effect

The following were prepared as curing agents.
Phenolic resin 1: aralkyl type phenolic resin having a hydroxyl equivalent weight of 176 g / eq and a softening point of 70 ° C. (trade name: Millex XL-225, manufactured by Mitsui Chemicals, Inc.)
Phenol resin 2: Biphenylene type phenol resin having a hydroxyl group equivalent of 199 g / eq and a softening point of 89 ° C. (product name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.)
Phenol resin 3: phenol novolak resin having a hydroxyl group equivalent of 106 g / eq and a softening point of 64 ° C. (product name H-4, manufactured by Meiwa Kasei Co., Ltd.)

The following compounds were prepared as curing accelerators according to the present invention.
Curing accelerator 1: Compound (iii) below
Curing accelerator 2: the following compound (iv)
Curing accelerator 3: the following compound (v)

Moreover, the following was prepared as a comparative hardening accelerator.
Curing accelerator A: Triphenylphosphine Curing accelerator B: Addition reaction product of triphenylphosphine and 1,4-benzoquinone

The following were prepared as inorganic fillers.
・ Fused silica: SO-25R manufactured by Admatechs, average particle size 0.6 μm
Fused silica: S430 manufactured by Micron, average particle size 19 μm

In addition, the following were prepared as various additives.
Coupling agent: Epoxy silane (γ-glycidoxypropyltrimethoxysilane)
Colorant: Carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation)
・ Release agent: Carnauba wax (manufactured by Celerica NODA)
・ Flame retardant: antimony trioxide

[Characteristic evaluation of epoxy resin composition]
The epoxy resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were evaluated by various tests shown below. The evaluation results are shown in Table 2. The epoxy resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours.

(1) Spiral flow (fluidity index)
An epoxy resin composition was molded under the above conditions using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) was measured. This is the initial flow distance (cm).

(2) Spiral flow survival rate (index of storage stability)
An epoxy resin composition that has been left in a constant temperature bath at 25 ° C. for 72 hours, 168 hours or 336 hours is molded under the conditions of (1) above, and the flow distance (cm) is measured. The ratio to the initial flow distance (cm) The survival rate was determined.

(3) Hardness upon heating The epoxy resin composition was molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and measured immediately using a Shore D type hardness meter after molding.

  As shown in Table 2, Examples 1 to 7 containing the curing accelerator according to the present invention have a higher spiral flow remaining rate after being left at room temperature (25 ° C.) than Comparative Examples 1 to 5, The result was excellent in storage stability. Moreover, the hardness at the time of Example 1-7 also became a high result compared with Comparative Examples 1-5.

Claims (5)

(A) an epoxy resin having two or more epoxy groups in one molecule, (B) a phenol resin having two or more phenolic hydroxyl groups in one molecule, and (C) the following general formula (I) A curing accelerator containing a phosphine compound, and (D) an inorganic filler ,
(C) In the following general formula (I), an epoxy resin composition in which the substitution position of the hydroxyl group of the benzene ring is para to the phosphorus atom .

[In Formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and m represents an integer of 1 to 3. Represent. ]   (A) The epoxy resin is a biphenylene type epoxy resin, a stilbene type epoxy resin, a sulfur atom-containing epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a salicylaldehyde type epoxy resin, a copolymer of naphthols and phenols The epoxy resin composition according to claim 1, comprising at least one epoxy resin selected from the group consisting of a type epoxy resin, an aralkyl type epoxy resin, a diphenylmethane type epoxy resin, and a triphenylmethane type epoxy resin.   (B) A group in which the phenol resin is composed of a biphenylene type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a copolymer type resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and a triphenylmethane type phenol resin. The epoxy resin composition of Claim 1 or Claim 2 containing the at least 1 sort (s) of phenol resin selected more.   (A) The epoxy resin contains a biphenyl type epoxy resin, and (B) the phenol resin is a biphenylene type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a benzaldehyde type phenol resin and an aralkyl type phenol resin. The epoxy resin composition according to claim 1, comprising at least one phenol resin selected from the group consisting of a polymerization type resin, a triphenylmethane type phenol resin, and a novolac type phenol resin. Elements,
The hardened | cured material of the epoxy resin composition of any one of Claims 1-4 which seals the said element,
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