TW202104339A - Encapsulating resin composition and electronic component device - Google Patents

Abstract

An encapsulating resin composition which comprises (A) an epoxy resin, (B) one or more hardeners, (C) a hardening accelerator, and (D) an inorganic filler, wherein the hardeners (B) include a hardener having a specific structure, the hardener with a specific structure having a softening point of 80-120 DEG C.

Description

Resin composition for sealing and electronic component device

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

In recent years, with the demand for higher functionality of electronic equipment, further miniaturization and thinning of semiconductor packages have continued to develop. For example, in a thin semiconductor package less than 1 mm, the thickness of the sealing material becomes 0.25 to 0.4 mm. If the thickness of the sealing material becomes thinner in this way, warpage occurs. If the semiconductor package is small and thin, it will have the following adverse effects: even a slight warpage will cause defects in the dicing step of singulating the package, or breakage due to the stress generated inside the package, etc. . Therefore, in order to reduce the warpage of the sealing material, measures have been taken to increase the coefficient of thermal expansion (for example, refer to Patent Documents 1 and 2). In addition, in packages with a large chip area such as semiconductor packages for memory applications, as a sealing material, resin properties with high thermal expansion and high elastic modulus at high temperatures are required. Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2017-128657 Patent Document 2: International Publication No. 2015/152037

[The problem to be solved by the invention]

As one of the measures to increase the coefficient of thermal expansion, the amount of filler can be reduced. However, if the amount of filler is reduced, although the coefficient of thermal expansion can be increased, the modulus of elasticity at high temperature is reduced, so there is a trade-off relationship between the two and it is difficult to have both. On the other hand, with the miniaturization of semiconductor packages, in order to release the generated heat to the outside, it is necessary to increase the thermal conductivity of the sealing material. In order to improve the thermal conductivity of the sealing material, high-density fillers are more effective. However, increasing the coefficient of thermal expansion and high-density filling are the opposite properties, so it is difficult to have both.

In addition, the epoxy resin composition for sealing described in Patent Document 1 uses a phenolic novolak resin having a specific structure as a curing agent. The phenolic novolak resin has a low softening point, and therefore has poor storage stability and poor moldability. full. Furthermore, a small and thin semiconductor package must have sufficient fluidity in order to fill the narrow part with the sealing material.

The present invention provides a resin composition for sealing, which has excellent fluidity, storage stability, and moldability, high thermal expansion, high elastic modulus at high temperatures, and a cured product with reduced warpage. In addition, the present invention provides an electronic component device using the resin composition for sealing. [Technical means to solve the problem]

The inventors of the present invention found that a sealing resin composition containing a hardener having a specific structure and a softening point in a specific range can solve the above-mentioned problems.

That is, the present invention relates to the following. [1] A resin composition for sealing, containing (A) epoxy resin, (B) curing agent, (C) curing accelerator, and (D) inorganic filler, wherein the (B) curing agent includes the following The curing agent represented by the general formula (1) has a softening point of 80 to 120°C for the curing agent represented by the following general formula (1).

(式中，R¹ ～R⁵ 分別獨立地為氫原子、烯丙基或鍵結至＊之單鍵，但R¹ ～R⁵ 之至少1個為烯丙基，複數個R¹ ～R⁵ 可相同，亦可分別不同，n為0～5之整數) [2]一種電子零件裝置，其具備藉由如上述[1]中記載之密封用樹脂組合物之硬化物予以密封之元件。 [發明之效果][化1]

(In the formula, R ¹ to R ⁵ are each independently a hydrogen atom, an allyl group, or a single bond bonded to *, but ^{at least one of R 1} to R ⁵ is an allyl group, and a plurality of R ¹ to R ⁵ It may be the same or different, and n is an integer of 0-5) [2] An electronic component device including an element sealed by a cured product of the sealing resin composition as described in [1] above. [Effects of Invention]

According to the present invention, it is possible to provide a sealing resin composition which is excellent in fluidity, storage stability, and moldability, has high thermal expansion, has a high elastic modulus at high temperature, and can obtain a cured product with reduced warpage. Furthermore, it is possible to provide an electronic component device using the resin composition for sealing.

Hereinafter, the present invention will be described in detail with reference to an embodiment.

＜Resin composition for sealing＞ The sealing resin composition of this embodiment contains (A) epoxy resin, (B) curing agent, (C) curing accelerator, and (D) inorganic filler, In addition, the curing agent (B) includes a curing agent represented by the following general formula (1), and the curing agent represented by the following general formula (1) has a softening point of 80 to 120°C.

(式中，R¹ ～R⁵ 分別獨立地為氫原子、烯丙基或鍵結至＊之單鍵，但R¹ ～R⁵ 之至少1個為烯丙基，複數個R¹ ～R⁵ 可相同，亦可分別不同，n為0～5之整數)。[化2]

(In the formula, R ¹ to R ⁵ are each independently a hydrogen atom, an allyl group, or a single bond bonded to *, but ^{at least one of R 1} to R ⁵ is an allyl group, and a plurality of R ¹ to R ⁵ It may be the same or different, and n is an integer of 0-5).

[(A) Epoxy] The (A) epoxy resin used in this embodiment may be one having two or more epoxy groups in one molecule, and its molecular weight, molecular structure, etc. are not particularly limited. (A) Epoxy resins include, for example, biphenyl type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy resins. Resins, bisphenol S-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenolmethane-type epoxy resin, epoxy resin containing tri-skeleton and other heterocyclic epoxy resins, stilbene-type bifunctional epoxy resin Resin, naphthalene type epoxy resin, condensed ring aromatic hydrocarbon modified epoxy resin, alicyclic epoxy resin, polyfunctional epoxy resin, etc. Among them, it can be biphenyl type epoxy resin, naphthalene type epoxy resin, and multifunctional epoxy resin. One type of these epoxy resins may be used, or two or more types may be mixed and used.

From the viewpoint of the rationality of the sealing resin composition and the melt viscosity during molding, the softening point of (A) epoxy resin may be 40-130°C, 50-110°C, or 80-110°C . Furthermore, the softening point in this specification refers to the "ring and ball softening point", which is the value measured in accordance with ASTM D36.

Examples of commercially available products of (A) epoxy resin include: YX-4000 (epoxy equivalent of 185, softening point 105°C) manufactured by Mitsubishi Chemical Corporation, YX-4000H (epoxy equivalent of 193) manufactured by the same company , Softening point 105℃), NC-3000 (epoxy equivalent 273, softening point 58℃) manufactured by Nippon Kayaku Co., Ltd., NC-3000H (epoxy equivalent 288, softening point 91℃) of the same company, DIC The company (stock) manufactures N-655EXP-S (epoxy equivalent 200, softening point 55°C) (all the above are trade names), etc.

The content of the (A) epoxy resin may be 2-10% by mass, or 4-10% by mass relative to the total amount of the resin composition for sealing. If the content of (A) epoxy resin is 2% by mass or more, the cured product can be molded, and if it is 10% by mass or less, a sufficient modulus of elasticity can be obtained.

[(B) Hardener] The curing agent (B) used in this embodiment includes a curing agent represented by the following general formula (1).

(式中，R¹ ～R⁵ 分別獨立地為氫原子、烯丙基或鍵結至＊之單鍵，但R¹ ～R⁵ 之至少1個為烯丙基，複數個R¹ ～R⁵ 可相同，亦可分別不同，n為0～5之整數)。[化3]

(In the formula, R ¹ to R ⁵ are each independently a hydrogen atom, an allyl group, or a single bond bonded to *, but ^{at least one of R 1} to R ⁵ is an allyl group, and a plurality of R ¹ to R ⁵ It may be the same or different, and n is an integer of 0-5).

The curing agent represented by the above general formula (1) has three or more hydroxyl groups and allyl groups in one molecule, and contains a triphenylmethane skeleton. Therefore, it is presumed that the (B) curing agent contains the curing agent represented by the general formula (1) to increase the crosslinking density, and even if the content of the (D) inorganic filler described later is increased, the thermal expansion coefficient can be increased. In addition, it is estimated that the cured product of the sealing resin composition of this embodiment can easily have a bending elastic modulus of E _{260 at 260} °C and 25°C without lowering the elastic modulus at high temperature. The ratio of the bending elastic modulus E _{25 (E 25} /E ₂₆₀ ) is set to 7.5 or less. It is estimated that the resin composition for sealing of the present embodiment can obtain a cured product with reduced warpage.

The carbon number of the allyl groups of ^{R 1} to R ^{5 may be 3-8, or 3-5.} Specific examples of allyl groups include -CH ₂ -CH=CH ₂ , -CH ₂ -C(CH ₃ )=CH ₂ and the like. In addition, a plurality of R ¹ to R ⁵ may be the same or different.

At least one of R ¹ to R ⁵ is an allyl group, and from the viewpoint of reactivity, the allyl group may be one of R ¹ to R ⁵ . Furthermore, in the above general formula (1), ^{at least one of R 1} to R ⁵ is an allyl group means that each benzene ring has at least one allyl group.

n is an integer of 0-5, may be an integer of 0-3, or an integer of 1-2.

The softening point of the hardener represented by the above general formula (1) is 80 to 120°C, may be 80 to 110°C, or may be 85 to 100°C. If the softening point of the hardener represented by the above general formula (1) is less than 80°C, the storage stability of the sealing resin composition may decrease, and if it exceeds 120°C, the manufacturability may decrease.

From the viewpoint of the storage stability of the sealing resin composition and the reduction of the warpage of the cured product, (B) the content of the curing agent represented by the general formula (1) contained in the curing agent may be 40% by mass or more, It may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 100% by mass.

As the (B) curing agent, the curing agent that can be used in combination with the curing agent represented by the above general formula (1) is not particularly limited, and examples thereof include resorcinol, catechol, bisphenol A, and bisphenol F , Substituted or unsubstituted biphenol and other phenolic compounds with two phenolic hydroxyl groups in one molecule; make phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F. Phenols such as phenylphenol and aminophenol and/or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicaldehyde, etc. Novolac-type phenol resin obtained by condensation or co-condensation under acid catalyst; phenol synthesized from the above-mentioned phenols and/or naphthols, dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc. Aralkyl type phenol resins such as aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin; p-xylylene modified phenol resin, m-xylylene modified phenol resin, melamine modified phenol Modified resins such as resins and terpene-modified phenol resins; dicyclopentadiene phenol resins and dicyclopentadiene naphthols synthesized from phenols and/or naphthols and dicyclopentadiene by copolymerization Resin; polycyclic aromatic ring modified phenol resin; biphenyl type phenol resin; triphenylmethane type phenol resin, etc. Furthermore, it may be a phenol resin obtained by copolymerizing two or more of the above-mentioned phenol resins. Among them, it may be an aralkyl type phenol resin, a biphenyl aralkyl type phenol, a novolak type phenol resin, a triphenylmethane type phenol resin, or an aralkyl type phenol resin or a biphenyl aralkyl type phenol.

From the viewpoint of manufacturability, the softening point of the (B) hardener may be 50 to 120°C, or 60 to 110°C.

The content of the (B) hardener may be 2-10% by mass, or 3-8% by mass relative to the total amount of the resin composition for sealing. If the content of the (B) curing agent is 2% by mass or more, the amount of the (D) inorganic filler does not become too much, and it is easy to knead the resin composition for sealing. In addition, the warpage of the cured product of the sealing resin composition can be reduced. On the other hand, if the content of (B) hardener is 10% by mass or less, the amount of (D) inorganic filler will not become too small, the elastic modulus of the hardened product of the sealing resin composition will increase, and warping can be reduced. Qu, can obtain practical hardened products.

[(C) Hardening accelerator] The (C) hardening accelerator used in this embodiment can be used without particular limitation as long as it is a hardening accelerator of epoxy resin for ordinary users. (C) Hardening accelerators include, for example, 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5, 5 ,6-Dibutylamino-1,8-diazabicyclo[5.4.0]undecene-7 and other cyclic amidine compounds; addition to these cyclic amidine compounds maleic anhydride, 1,4- Benzoquinone, 2,5-methylbenzoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5- Compounds with π-bonds such as quinone compounds such as methyl-1,4-benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane, phenol resins and other compounds with π-bonds; Tertiary amine compounds such as benzylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol and their derivatives; 2-methylimidazole, 2-ethylimidazole, 2-benzimidazole, 2- Ethyl-4-methimidazole, 2-phenyl-4-methimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethimidazole, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 2,4-Diamino-6-[2'-Methylimidazolyl-(1')]-Ethyl-Symmetric Tris, 2,4-Diamino-6-[2' -Undecylimidazolyl-(1')]-Ethyl-Symmetric Tris, 2,4-Diamino-6-[2'-Ethyl-4'-Methylimidazolyl-(1') ]-Ethyl-Symmetric Tris, and other imidazole compounds with imidazole ring-Symmetric silicon-containing Tris compounds and other imidazole compounds and their derivatives; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, Tris (4-methylphenyl) phosphine, diphenyl phosphine, phenyl phosphine and other organic phosphine compounds; addition of maleic anhydride, 1,4-benzoquinone, 2,5-methane to these organic phosphine compounds Benzoquinone, 1,4-Naphthoquinone, 2,3-Dimethylbenzoquinone, 2,6-Dimethylbenzoquinone, 2,3-Dimethoxy-5-methyl-1,4-benzene Quinone, phenyl-1,4-benzoquinone and other quinone compounds, diazophenylmethane, phenol resins and other compounds with π bonds are phosphorus compounds with polarization in the molecule; tetraphenylphosphonium tetraphenylborate, Tetraphenyl phosphonium ethyl triphenyl borate, tetrabutyl phosphonium tetrabutyl borate and other tetra-substituted phosphonium-tetra-substituted borate; 2-ethyl-4-methylimidazole-tetraphenyl borate, N-methyl 𠰌 Tetraphenyl boron salts such as phyllo-tetraphenyl borate and their derivatives. (C) One type of hardening accelerator may be used, or two or more types may be mixed and used.

(C) As the hardening accelerator, an imidazole-based hardening accelerator can be used among them. In particular, the resin composition for sealing is excellent in fluidity by blending the above-mentioned imidazole compound.

The content of the (C) hardening accelerator may be 0.1 to 3% by mass, or 0.1 to 1% by mass relative to the total amount of the resin composition for sealing. (C) If the content of the hardening accelerator is 0.1% by mass or more, the effect of accelerating the hardenability is obtained, and if it is 3% by mass or less, the filling properties can be improved.

[(D) Inorganic fillers] The (D) inorganic filler used in this embodiment can be used without particular limitation as long as it is an inorganic filler generally used in a resin composition for sealing. (D) Inorganic fillers, specifically, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, barium titanate, silicon carbide, nitride Powders such as silicon, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, forsterite, talc, spinel, mullite, titanium oxide, spheroidized particles, single crystal fiber, glass Fiber etc. (D) One type of inorganic filler may be used, or two or more types may be mixed and used.

From the viewpoint of improving mechanical strength, (D) the inorganic filler can be fused silica or crystalline silica. From the viewpoint of increasing the thermal conductivity, (D) the inorganic filler may be alumina, and from the viewpoint of increasing the dielectric constant, it may be barium titanate.

(D) The average particle size of the inorganic filler may be 5-12 μm or 5-10 μm. (D) If the average particle diameter of the inorganic filler is 5 μm or more, the filling property of the sealing resin composition can be improved, and if it is 12 μm or less, the fluidity and moldability of the sealing resin composition can be improved. In addition, in this embodiment, the so-called average particle size means the particle size when the cumulative size from the small diameter side becomes 50% in the volume-based particle size distribution obtained by the laser diffraction scattering particle size distribution measuring device ( D50).

In addition, (D) the maximum particle size of the inorganic filler may be 15 to 75 μm, or 15 to 55 μm. If (D) the maximum particle size of the inorganic filler is 75 μm or less, the filling property can be improved. In addition, the maximum particle size in this embodiment means the particle size (D99) at which the accumulation from the small diameter side in the volume-based particle size distribution becomes 99%.

From the viewpoint of improving fluidity, (D) the shape of the inorganic filler may be spherical.

The content of the (D) inorganic filler may be 75 to 95% by mass, 80 to 90% by mass, or 83 to 90% by mass relative to the total amount of the resin composition for sealing. If the content of (D) the inorganic filler is 75% by mass or more, the elastic modulus of the cured product of the sealing resin composition can be maintained high, and if it is 95% by mass or less, the moldability can be improved.

In addition to the above components, the resin composition for sealing of this embodiment can also be blended with flame retardants, carbon black, organic dyes, titanium oxide, iron oxide and other colorants, mold release agents, and couplers that are usually blended in this composition. Additives such as mixtures and ion trapping agents. When the resin composition for sealing of this embodiment contains the above-mentioned additives, the compounding amount may be 0.1 to 1% by mass, or 0.2 to 0.5% by mass relative to the total amount of each resin composition for sealing.

In the sealing resin composition of the present embodiment, the content of the above-mentioned components (A) to (D) may be 80% by mass or more, 90% by mass or more, or 95% by mass or more.

When preparing the sealing resin composition of this embodiment, it is only necessary to mix (A) epoxy resin, (B) hardener, (C) hardening accelerator, (D) inorganic filler, and other as needed by a mixer or the like After the various ingredients are fully mixed (dry blending), they are melted and kneaded by a kneading device such as a hot roll and a kneader, and then pulverized to an appropriate size after cooling.

Aspect of this embodiment the seal bending elastic modulus E of 260 ℃ at _260. The cured resin composition of the bending at 25 deg.] C the ratio of the elastic modulus E of ₂₅ (E ₂₅ / E ₂₆₀₎ may be 7.5 or less, may Below 7.0. If the ratio (E ₂₅ /E ₂₆₀ ) is 7.5 or less, the warpage of the hardened material can be reduced, and a highly reliable electronic component device can be obtained.

_{The flexural modulus E 260} of the cured product of the sealing resin composition of this embodiment at 260°C may be 1.4 to 3.5 GPa, or 1.8 to 3.3 GPa. If the above-mentioned E ₂₆₀ is within the above-mentioned range, the easy-satisfaction ratio (E ₂₅ /E ₂₆₀ ) is 7.5 or less. Furthermore, by appropriately adjusting the ratio and type of resin components in the resin composition for sealing, the value of the _{above-mentioned E 260 can be adjusted. In addition, the flexural modulus E 25} of the cured product of the sealing resin composition of this embodiment at 25° C. may be 12 to 30 GPa, or 14 to 25 GPa. If the above-mentioned E ₂₅ is within the above-mentioned range, the easy-satisfaction ratio (E ₂₅ /E ₂₆₀ ) is 7.5 or less. Furthermore, by appropriately adjusting the content of the (D) inorganic filler, the value of the _{above-mentioned E 25 can be adjusted.} The above-mentioned bending elastic modulus E ₂₅ and E ₂₆₀ can be measured in accordance with JIS K6911: 2006, and specifically, can be measured by the method described in the examples.

The thermal expansion coefficient (α1) of the cured product of the sealing resin composition of this embodiment may be 7-18 ppm/°C, or 9-16 ppm/°C. In addition, the thermal expansion coefficient (α2) of the cured product of the resin composition for sealing may be 33 to 70 ppm/°C, or 35 to 60 ppm/°C. The thermal expansion coefficient can be measured by thermal mechanical analysis (Thermal Mechanical Analysis: TMA), and specifically, can be measured by the method described in the examples.

From the viewpoint of improving moldability, the glass transition temperature of the cured product of the sealing resin composition of the present embodiment may be 150°C or higher, or may be 155°C or higher. In addition, if the glass transition temperature of the cured product is 150°C or higher, it is easy to satisfy the ratio (E ₂₅ /E ₂₆₀ ) of 7.5 or less. In addition, continuous formability is improved. The glass transition temperature (Tg) can be measured by thermal mechanical analysis (Thermal Mechanical Analysis: TMA), and specifically, can be measured by the method described in the examples.

＜Electronic component device＞ The electronic component device of this embodiment is equipped with the element sealed by the hardened|cured material of the said resin composition for sealing. The above-mentioned electronic component devices refer to supporting members such as lead frames, single crystal silicon semiconductor components or compound semiconductor components such as SiC and GaN, metal wires, bumps and other components used to connect these electrical connections, and a complete set of other components. An electronic component device in which necessary parts are sealed by the cured product of the above-mentioned sealing resin composition.

Fig. 1 shows an example of the electronic component device of this embodiment. An adhesive layer 3 may be interposed between the lead frame 1 such as a copper frame and the semiconductor element 2. Moreover, the electrode 4 on the semiconductor element 2 and the lead part 5 of the lead frame 1 are connected by the bonding wire 6, and these are further sealed by the hardened|cured material 7 of the resin composition for sealing of this embodiment.

As a method of sealing using the above-mentioned resin composition for sealing, the transfer molding method is most commonly used, but an injection molding method, a compression molding method, etc. may also be used. The forming temperature can be 150-220°C, or 170-210°C. The forming time can be 45 to 300 seconds, or 60 to 200 seconds. In the case of post-curing, the heating temperature is not particularly limited. For example, it may be 150 to 220°C or 170 to 210°C. Moreover, heating time is not specifically limited, For example, it may be 0.5-10 hours, and may be 1-8 hours. Example

Next, the present invention will be described in detail with examples, but the present invention is not limited by these examples.

(Examples 1 to 7 and Comparative Examples 1 to 5) Use a mixer at room temperature (23°C) to mix the components listed in Table 1 and their blending amounts, heat and knead at 90-115°C using a hot roller, cool and pulverize to prepare sealing resin combination. Furthermore, in Table 1, an empty column means that it has not been deployed.

The details of each component described in Table 1 used when preparing the resin composition for sealing are as follows.

[(A) Epoxy] ・YX-4000: Biphenyl type epoxy resin (trade name, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185, softening point 105°C) ・NC-3000: Biphenol novolac epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 273, softening point 58°C) ・N-655EXP-S: o-cresol novolac epoxy resin (trade name, manufactured by DIC Corporation, epoxy equivalent 200, softening point 55°C)

[(B) Hardener] (The hardener represented by the general formula (1)) ・SH-041-01: Triphenylmethane type phenol resin containing allyl groups (trade name, manufactured by Meiwa Chemical Co., Ltd., hydroxyl equivalent 139, softening point 90°C) (Hardeners other than the hardener represented by the general formula (1)) ・MEH-7500: Triphenylmethane-type phenol (trade name, manufactured by Meiwa Chemical Co., Ltd., hydroxyl equivalent 98, softening point 110°C) ・MEH-5000: Phenolic novolac resin (trade name, manufactured by Meiwa Chemical Co., Ltd., hydroxyl equivalent 168, softening point 73°C) ・MEHC-7800SS: Aralkyl phenol resin (trade name, manufactured by Meiwa Chemical Co., Ltd., hydroxyl equivalent 172, softening point 65°C)

[(C) Hardening accelerator] ・2P-4MHZ: Imidazole compound (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.)

[(D) Inorganic fillers] ・FB-910GSQ: Spherical fused silica (trade name, manufactured by Admatechs Co., Ltd., average particle size 5 μm, maximum particle size 20 μm)

[Other ingredients] ・Release agent: Carnauba wax (trade name: manufactured by Toyo-adl Co., Ltd.) ・Colorant: MA-100RMJ (trade name: manufactured by Mitsubishi Chemical Corporation) ・Flame retardant: FP-100 (trade name: manufactured by FUSHIMI Pharmaceutical Co., Ltd.) ・Ion scavenger: DHT-4C (trade name: manufactured by Kyowa Chemical Industry Co., Ltd.)

The measurement and evaluation of the characteristics of the resin composition for sealing prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were performed under the measurement conditions shown below. The evaluation results are shown in Table 1.

[Evaluation item] (1) Glass transition temperature, thermal expansion coefficient (α1, α2) The resin composition for sealing obtained was molded by a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 7 MPa, and a curing time of 120 seconds, and then cured at a temperature of 175°C for 8 hours to produce a trial Pieces (3 mm×4 mm×17 mm). The obtained test piece was used for measurement in a thermal analysis device (manufactured by Seiko Instruments, product name: TMA/SS150) under the conditions of a temperature increase rate of 10° C./min and a load of 98 mN. The thermal expansion coefficients at 40～90℃ and 200～230℃ of the obtained TMA curve are set to α1 and α2, respectively, and the temperature at the intersection of the TMA curve and the wiring at 90℃ and 190℃ is read, and the temperature is set as glass Transition temperature (Tg).

(2) Bending elastic modulus (E ₂₅ , E ₂₆₀ ) and ratio (E ₂₅ /E ₂₆₀ ) Make test pieces (4 mm×10 mm×80 mm) under the same conditions as in (1) above. The obtained test pieces were used to measure the bending elastic modulus (E ₂₅ ) at 25° C. and the bending elastic modulus (E ₂₆₀ ) at 260° C. respectively. The measurement system uses a precision universal testing machine (manufactured by Shimadzu Corporation, Autograph AG-IS, a fulcrum punch with a radius of 0.3 mm, and a test speed of 1 mm/min) and a load is applied, and it is calculated in accordance with JIS-K6911:2006. Furthermore, the ratio (E ₂₅ /E ₂₆₀ ) is calculated based on the above-mentioned E ₂₅ and E _260.

(3) Gel time The sealing resin composition obtained is expanded into a circle with a diameter of 3 to 5 cm on a hot plate maintained at 175°C. When kneading at a constant speed, the sealing resin composition increases viscosity, and the final viscosity loss is measured. time.

(4) Spiral flow length The spiral flow length was measured by subjecting the obtained sealing resin composition to transfer molding under the conditions of a molding temperature of 175°C and a molding pressure of 7 MPa.

(5) Specific gravity The volume and mass of the obtained sealing resin composition are measured, and the specific gravity of the sealing resin composition is calculated based on the result.

(6) Flow viscosity According to JIS K 7210: 1999, the viscosity of the obtained sealing resin composition was measured using a Koka type rheometer (manufactured by Shimadzu Corporation, product name: CFT-500C).

(7) Shrinkage rate The test piece was produced under the same conditions as in (1) above. Using the obtained test piece, in accordance with JIS K 6911: 2006, the shrinkage rate (%) was obtained by the following formula (i). Shrinkage rate (%)=((D－d)/D)×100 (i) In the formula, D: the length of the cavity of the mold (mm), d: the length of the test piece (mm).

(8) Warpage (room temperature (25℃), 260℃) The prepared sealing resin composition was used to produce an evaluation package (15 mm×15 mm, sealing thickness: 250 μm, total thickness: 380 μm) mounted with a chip of 10 mm×10 mm and 150 μm in thickness. The following test was carried out: After curing treatment at 175°C for 8 hours, it was placed in a heating device and the temperature in the device was raised from 25°C (heating rate 10°C/25 seconds), and the temperature was lowered after reaching 260°C (cooling rate) 10°C/25 seconds) to 25°C. The state of the warpage of the package for evaluation at 260°C after the above temperature rise and the maximum height (μm) of the warpage from the ground surface were measured. In addition, the state of the warpage of the package for evaluation at 25°C after the temperature drop and the maximum height (μm) of the warpage from the ground surface were measured. The maximum height in the case of smile type warping is negative, and the maximum height of cry type warping is positive, and the evaluation is based on the following criteria. A: The absolute value of the resulting warpage is less than 2 mm C: The absolute value of the generated warpage is 2 mm or more

(9) Storage stability The resin composition for sealing is stored at room temperature (25°C) and 40% relative humidity for 24 hours and then taken out. The mass of the block is measured, and the mass of the block is relative to the mass of the entire resin composition for sealing. The ratio is expressed. In addition, 20% or less is regarded as a pass.

(10) Continuous formability Use a demolding load measuring forming machine (manufactured by Kyocera Corporation, trade name: GM-500) to PBGA (Plastic Ball Grid Array, 30 mm×30 mm×1 mm, t/2 holes) Continuous molding with 300 shots. The mold temperature was set to 190°C, and the molding time was set to 240 seconds. In addition, evaluation was performed based on the following criteria. A: It can be molded continuously to 150 shots, and there is no mold dirt. B: Although mold dirt is found, it can be molded continuously up to 150 shots C: Continuous molding to 150 shots cannot be achieved due to sticking to the mold, etc.

[Table 1] Table 1 unit Example Comparative example 1 2 3 4 5 6 7 1 2 3 4 5 Resin composition for sealing (A) Epoxy resin YX-4000 Mass parts 4.32 4.43 4.43 3.68 4.43 4.93 5.70 4.53 4.86 4.10 4.00 4.10 NC-3000 Mass parts 3.24 3.35 2.75 3.32 3.67 3.02 3.02 3.02 N-655EXP-S Mass parts 3.35 3.35 3.70 (B) Hardener represented by general formula (1) SH-041-01 Mass parts 4.86 5.72 5.72 4.65 3.78 4.65 2.15 Hardeners other than the hardener represented by the general formula (1) MEH-7500 Mass parts 1.94 2.16 2.15 3.67 4.23 MEH-5000 Mass parts 1.00 5.65 5.30 2.15 MEHC-7800SS Mass parts 1.08 1.30 1.08 6.48 (C) Hardening accelerator 2P-4MHZ Mass parts 0.40 0.40 0.40 0.32 0.40 0.46 0.40 0.40 0.40 0.40 0.40 0.40 (D) Inorganic filler FB-910GSQ Mass parts 85.0 85.0 85.0 87.5 85.0 83.0 87.5 85.0 85.0 85.0 85.0 85.0 Release agent Carnauba wax Mass parts 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Colorant MA-100RMJ Mass parts 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Flame retardant FP-100 Mass parts 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Ion scavenger DHT-4C Mass parts 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 total Mass parts 100 100 100 100 100 100 100 100 100 100 100 100 (D) The content of inorganic filler relative to the total amount of the resin composition quality% 85.0 85.0 85.0 87.5 85.0 83.0 87.5 85.0 85.0 85.0 85.0 85.0 (B) The content of the hardener represented by the general formula (1) contained in the hardener quality% 81.8 100.0 100.0 100.0 66.1 68.3 40.6 0.0 0.0 0.0 0.0 0.0 characteristic Glass transition temperature (Tg) °C 150 158 172 155 168 163 160 146 169 148 130 154 Coefficient of thermal expansion (α1) ppm/℃ 13 13 12 10 12 14 9 13 11 12 12 11 Coefficient of thermal expansion (α2) ppm/℃ 53 53 50 42 52 61 39 55 43 46 47 44 Bending elastic modulus E ₂₅ (25℃) GPa 17.8 19.5 20.0 22.0 19.2 16.4 22.0 20.0 20.0 20.0 19.0 19.9 Bending elastic modulus E ₂₆₀ (260℃) GPa 2.4 2.8 2.7 3.3 2.6 2.2 3.0 2.2 1.2 2.1 0.5 1.5 Gel time second 52 50 53 53 51 52 49 53 53 50 54 50 Spiral flow length cm 150 155 147 151 145 140 123 138 139 142 200 141 proportion - 1.95 1.95 1.95 1.98 1.96 1.92 1.98 1.96 1.96 1.95 1.95 1.96 Flow viscosity Pa•s 12 13 14 12 10 8 7 11 14 13 8 13 Shrinkage % 0.28 0.3 0.24 0.27 0.25 0.29 0.22 0.29 0.15 0.27 0.19 0.18 Warpage 25℃ - A A A A A A A A C A C C Warpage 260℃ - A A A A A A A C C C C C Ratio (E ₂₅ /E ₂₆₀ ) - 7.42 6.96 7.41 6.67 7.38 7.45 7.33 9.09 16.67 9.52 38.00 13.27 Storage stability - 4 3 7 6 4 5 10 twenty one 12 twenty four 30 11 Continuous formability - A A B A B B B B B B C B

It can be seen that the sealing resin compositions of Examples 1 to 7 using the curing agent (B) containing the curing agent represented by the general formula (1) are excellent in fluidity, storage stability, and continuous moldability, and satisfy the ratio (E ₂₅ /E ₂₆₀ ) is 7.5 or less, high thermal expansion and high elastic modulus at high temperature, and can obtain hardened products with reduced warpage. On the other hand, it can be seen that the sealing resin compositions of Comparative Examples 1 to 5 that do not contain the curing agent represented by the general formula (1) as the curing agent do not satisfy the ratio (E ₂₅ /E ₂₆₀ ) of 7.5 or less, and the cured product The warpage is large. Furthermore, although the sealing resin composition of Comparative Example 1 using phenolic novolak resin (MEH-5000) as the hardener has a low viscosity of 11 Pa·s, the spiral flow length is short, 138 cm, and it has There is a risk of unfilled parts in the molded product.

1: Lead frame 2: Semiconductor components 3: Adhesive layer 4: electrode 5: Lead part 6: Bonding wire 7: Hardened product of resin composition for sealing

Fig. 1 is a cross-sectional view showing an electronic component device according to an embodiment of the present invention.

Claims (6)

A resin composition for sealing, which contains (A) epoxy resin, (B) curing agent, (C) curing accelerator, and (D) inorganic filler, wherein the (B) curing agent includes the following general formula ( 1) The hardening agent represented by the following general formula (1) has a softening point of 80 to 120°C; [化1]

(In the formula, R ¹ to R ⁵ are each independently a hydrogen atom, an allyl group, or a single bond bonded to *, but ^{at least one of R 1} to R ⁵ is an allyl group, and a plurality of R ¹ to R ⁵ It may be the same or different, and n is an integer of 0-5). The resin composition for sealing according to claim 1, wherein the content of the curing agent represented by the general formula (1) contained in the curing agent (B) is 40% by mass or more. The sealing item 1 or 2 request with a resin composition, wherein the curved under the 260 ℃ curing the encapsulating resin composition of the composition of the modulus of elasticity E _260. curved under the 25 deg.] C elastic modulus E ratio of ₂₅ of (E ₂₅ /E ₂₆₀ ) is 7.5 or less. The resin composition for sealing according to any one of claims 1 to 3, wherein the glass transition temperature of the cured product of the resin composition for sealing is 150°C or higher. The resin composition for sealing according to any one of claims 1 to 4, wherein the content of the above-mentioned (D) inorganic filler is 75 to 95% by mass relative to the total amount of the resin composition for sealing. An electronic component device provided with an element sealed by a cured product of the sealing resin composition according to any one of claims 1 to 5.

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