JP7251583B2 - Sealing resin composition, cured product, electronic component device, and method for manufacturing electronic component device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sealing resin composition, a cured product, an electronic component device, and a method for producing an electronic component device.

In recent years, there has been a demand for high integration of electronic components such as semiconductor chips. For example, flip-chip packages in which a semiconductor chip and a substrate are bonded with solder bumps are often used for semiconductor modules.
Such semiconductor modules are mounted in compact mobile devices such as mobile phones and smart phones, and their demand in the market is increasing year by year. An underfill material is used as a sealing material in the flip chip package to ensure its insulation. Since the underfill material exhibits fluidity at room temperature, the gap between the chip and the substrate is filled by using capillary action, and then the underfill material is cured to obtain sealing properties of the flip chip package.

In the manufacturing process of such a semiconductor module, when curing an uncured underfill material, there is a problem that a highly fluid component contained in the underfill material bleeds out from the underfill material. When the bleeding phenomenon occurs, the highly fluid component exuded from the underfill material contaminates the wiring on the substrate, and there is a problem that the reliability and bondability of the semiconductor module are lowered.

As a method for eliminating the bleeding phenomenon, for example, epoxy resin (A) having a number average molecular weight of 600 to 1000, curing agent (B), organic solvent (C), coupling agent (D) and inorganic filler (E) A method of using an insulating paste of the following type is disclosed (for example, Patent Document 1).

JP-A-2000-178342

However, in recent years, electronic components such as semiconductor chips are increasingly required to be miniaturized, and the distance to wiring arranged around the electronic components is becoming shorter. In a semiconductor module having such miniaturized electronic components, the method described in Patent Document 1 is not sufficient to suppress the occurrence of the bleeding phenomenon, and a composition capable of more strictly suppressing the occurrence of the bleeding phenomenon is desirable.

Here, the bleeding phenomenon occurs when highly fluid components ooze out onto the surface of the solder resist substrate applied to the semiconductor module, and the degree of oozing of the highly fluid components in the bleeding phenomenon depends on the type of substrate. also depends. In addition, when the substrate surface is plasma-treated, the bleeding phenomenon is particularly likely to occur. Therefore, from the viewpoint of suppressing the bleeding phenomenon, it is preferable not to perform the plasma treatment on the substrate surface. However, since plasma treatment is used to clean the substrate surface in the pre-sealing process of the semiconductor module, it is often unavoidable in terms of manufacturing. It is desirable to be able to suppress the occurrence.

One aspect of the present invention is a sealing resin composition capable of suppressing the occurrence of a bleeding phenomenon, a cured product obtained by curing the sealing resin composition, an electronic component device comprising the cured product, and the sealing An object of the present invention is to provide a method for manufacturing an electronic component device using a resin composition.

In order to achieve the above objects, the present inventors have made intensive studies and found that a resin composition for sealing that can suppress the occurrence of the bleeding phenomenon by using a resin containing a phenoxy structure in the resin composition for sealing. I found what I got.

Specific means for achieving the above object are as follows.

<1> A sealing resin composition comprising (A) an epoxy resin, (B) a curing agent having at least one amino group, (C) a resin having a phenoxy structure, and (D) an inorganic filler.
<2> The encapsulating resin composition according to <1>, wherein (C) the resin having a phenoxy structure has a weight average molecular weight (M _w ) of 500 or more and 100,000 or less.
<3> The encapsulating resin composition according to <1>, wherein (C) the resin having a phenoxy structure has a weight average molecular weight (M _w ) of 2,000 or more and 100,000 or less.
<4> The encapsulating resin composition according to any one of <1> to <3>, wherein (C) the resin having a phenoxy structure contains a compound represented by the following general formula (1).

(In the general formula (1), A represents a structure represented by the general formula (2), and the terminal group B represents a hydroxyl group or a group represented by the general formula (3). In the general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, n represents an integer of 1 to 1000. When n is an integer of 2 or more, two or more A may be the same or different. The two terminal groups B may be the same or different.)
<5> Any one of <1> to <4>, wherein the content of (C) the resin having a phenoxy structure is 0.05% by mass to 2.0% by mass with respect to the resin composition for sealing 2. The encapsulating resin composition according to 1.
<6> The encapsulating resin composition according to any one of <1> to <5>, which is used for encapsulating an electronic component device.

<7> A cured product obtained by curing the encapsulating resin composition according to any one of <1> to <6>.

<8> A substrate having a circuit layer, an electronic component disposed on the substrate and electrically connected to the circuit layer, and the electronic component according to <7> disposed in a gap between the substrate and the electronic component. An electronic component device comprising: a cured product;

<9> A substrate having a circuit layer, and an electronic component disposed on the substrate and electrically connected to the circuit layer are bonded to each other for sealing according to any one of <1> to <6>. A method for manufacturing an electronic component device, comprising a step of sealing using a resin composition.

According to one aspect of the present invention, a sealing resin composition capable of suppressing the occurrence of a bleeding phenomenon, a cured product obtained by curing the sealing resin composition, an electronic component device comprising the cured product, and the sealing It is possible to provide a method for manufacturing an electronic component device using the sealing resin composition.

DETAILED DESCRIPTION OF THE INVENTION Embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present invention.
In the present disclosure, the term "process" includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .
In the present disclosure, the numerical range indicated using "-" includes the numerical values before and after "-" as the minimum and maximum values, respectively.
In the numerical ranges described step by step in the present disclosure, the upper limit value or lower limit value described in one numerical range may be replaced with the upper limit value or lower limit value of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present disclosure, when there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component in the composition is means the total content or content of
In the present disclosure, the particle size of each component in the composition refers to a mixture of the plurality of types of particles present in the composition when there are multiple types of particles corresponding to each component in the composition, unless otherwise specified. means the value of
In the present disclosure, the term “layer” includes the case where the layer is formed in the entire region when observing the region where the layer exists, and the case where it is formed only in part of the region. be

[Resin composition for encapsulation]
The encapsulating resin composition of the present disclosure includes (A) an epoxy resin, (B) a curing agent having at least one amino group, (C) a resin having a phenoxy structure, and (D) an inorganic filler. The encapsulating resin composition can be used, for example, for encapsulating electronic components. The encapsulating resin composition can suppress the occurrence of the bleeding phenomenon. The reason for this is presumed as follows.

The phenoxy resin contained in the encapsulating resin composition has a high affinity with highly fluid components that can cause bleeding. Therefore, when the encapsulating resin composition is applied onto the substrate, separation of part of the encapsulating resin composition onto the substrate is suppressed, and the occurrence of the bleeding phenomenon is considered to be suppressed. In addition, even when a liquid component such as an epoxy resin that is liquid at 25° C. is contained as a highly fluid component in the encapsulating resin composition, the phenoxy resin and the liquid component have a high affinity, so bleeding is preferable. It is considered that the occurrence of the phenomenon is suppressed.

Further, when the substrate surface is plasma-treated, the bleeding phenomenon is likely to occur. However, by using the aforementioned encapsulating resin composition, the bleeding phenomenon can be suppressed even when the substrate surface is plasma-treated.

Each component contained in the encapsulating resin composition will be described below.

<(A) Epoxy resin>
The encapsulating resin composition of the present disclosure contains (A) an epoxy resin. (A) The epoxy resin imparts curability and adhesiveness to the encapsulating resin composition, and imparts durability and heat resistance to the cured product of the encapsulating resin composition.

(A) The epoxy resin preferably contains an epoxy resin that is liquid at 25° C. from the viewpoint of fluidity. In addition, an epoxy resin that is solid at 25°C may be used in combination, and it is preferable to use an epoxy resin that is solid at 25°C within a range that does not affect the fluidity of the encapsulating resin composition.
In the present disclosure, for each component contained in the encapsulating resin composition, those having a viscosity of 50 Pa·s or less at 25°C are referred to as “liquid at 25°C”.
(A) By including an epoxy resin that is liquid at 25°C as the epoxy resin, the fluidity of the encapsulating resin composition tends to be improved.

(A) The viscosity of the epoxy resin at 25° C. is preferably 50 Pa·s or less, more preferably 0.01 Pa·s to 40 Pa·s, and 0.5 Pa·s to 30 Pa·s. is more preferred.
In the present disclosure, the viscosity at 25° C. of each component contained in the encapsulating resin composition such as (A) epoxy resin was measured at 25° C. and 10 rotations using an E-type viscometer (cone angle 3°). Refers to the value measured under the condition of revolutions/minute.

(A) The type of epoxy resin is not particularly limited. Epoxy resins include naphthalene type epoxy resins; diglycidyl ether type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S and hydrogenated bisphenol A; phenols and aldehydes represented by orthocresol novolac type epoxy resins. Glycidyl ester type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; Obtained by reacting amine compounds such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin. and glycidylamine type epoxy resins.

(A) The epoxy equivalent of the epoxy resin is preferably 80 g/eq to 250 g/eq, more preferably 85 g/eq to 240 g/eq, and 90 g/eq to 230 g/eq, from the viewpoint of viscosity adjustment. is more preferable.
A method for measuring the epoxy equivalent in the present disclosure is described below.
Epoxy resin is dissolved in methyl ethyl ketone. Glacial acetic acid, cetyltrimethylammonium bromide, and screen indicator (prepared by mixing a solution of 0.3 g of patent blue dissolved in 100 mL of glacial acetic acid and a solution of 1.5 g of thymol blue dissolved in 500 mL of methanol) as a solution. was added and titrated with a perchloric acid solution adjusted to 0.1N. Also, a blank test is performed, and the epoxy equivalent is calculated from the following formula.
Epoxy equivalent (g / eq) = (1000 × W) / {(SB) × N}
W: sample mass B: amount of 0.1N perchloric acid solution used for blank test S: amount of 0.1N perchloric acid solution used for sample titration N: normality of perchloric acid solution (0.1N )

(A) The weight average molecular weight of the epoxy resin is not particularly limited. (A) The weight average molecular weight of the epoxy resin is preferably 100 to 1,000, more preferably 150 to 800, even more preferably 200 to 500.
Methods for measuring weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure are described below.
The weight average molecular weight and number average molecular weight are derived by measuring by gel permeation chromatography (GPC) and converting using a standard polystyrene calibration curve. The conditions of GPC are as shown below.
-GPC conditions-
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: 3 in total below ・Gelpack GL-R420
・Gelpack GL-R430
・Gelpack GL-R440
(Above, manufactured by Hitachi Chemical Co., Ltd., product name)
Eluent: Tetrahydrofuran Measurement temperature: 25°C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

(A) You may use a commercial item as an epoxy resin. Commercially available (A) epoxy resins include Nippon Steel & Sumikin Chemical Co., Ltd. bisphenol F type epoxy resin (product name: YDF-8170C), Nippon Steel & Sumikin Chemical Co., Ltd. bisphenol A type epoxy resin (product name: YD-128), Mitsui Chemical Co., Ltd. bisphenol A type epoxy resin (product name: R-140P), Mitsubishi Chemical Corporation amine type epoxy resin (product name: jER-630), DIC Corporation naphthalene type epoxy resin (product name: HP-4032), etc. mentioned. (A) The epoxy resin is not limited to these specific examples. (A) An epoxy resin may be used individually by 1 type, or may use 2 or more types together.

(A) The content of the epoxy resin is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass, and 20% by mass with respect to the resin composition for sealing. More preferably, it is up to 35% by mass.

<(B) Curing agent having at least one amino group (specific curing agent)>
The encapsulating resin composition of the present disclosure includes (B) a curing agent having at least one amino group (hereinafter also referred to as “(B) specific curing agent”). (B) The specific curing agent tends to be able to prepare a sealing resin composition with excellent fluidity and pot life compared to other curing agents described later.

(B) The specific curing agent is not particularly limited as long as it can cure the (A) epoxy resin. (B) The specific curing agent may be one that cures by polymerization together with the epoxy resin. Either liquid or solid at 25° C. can be used. (B) By including a curing agent that is liquid at 25° C. as the specific curing agent, the fluidity of the encapsulating resin composition tends to be improved.

(B) Specific curing agents include amine-based curing agents such as chain aliphatic amines, cyclic aliphatic amines, aliphatic aromatic amines, and aromatic amines. As the amine-based curing agent, aromatic amines are preferable from the viewpoint of heat resistance and electrical properties.

Specific examples of amine curing agents include m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, and 3,5-diethyl-2,4-diaminotoluene. , 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole, aromatic amine curing agents having one aromatic ring; 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl- Aromatic amine curing agents having two aromatic rings such as 4,4'-diaminodiphenylmethane and 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane; hydrolytic condensation of aromatic amine curing agents Aromatic amines having a polyether structure such as polytetramethylene oxide di-p-aminobenzoate and polytetramethylene oxide di-p-aminobenzoate; Condensates of aromatic diamines and epichlorohydrin; Aromatic diamines and Examples include reaction products with styrene.

(B) A commercial product may be used as the specific curing agent. Commercially available (B) specific curing agents include Nippon Kayaku Co., Ltd. amine curing agent (product name: Kayahard-AA), Mitsubishi Chemical Corporation amine curing agent (product name: jER Cure (registered trademark) W, jER Cure (registered trademark) 113, etc.), an amine curing agent manufactured by Albermarle Japan Co., Ltd. (product name: Etacure 300), and the like. (B) The specific curing agent is not limited to these specific examples. (B) Specific curing agents may be used alone or in combination of two or more.

The content ratio of (A) the epoxy resin and (B) the specific curing agent in the encapsulating resin composition is not particularly limited. The ratio to the number of equivalents of amino groups contained is also not particularly limited. In order to keep each unreacted amount small, the ratio of the number of equivalents of amino groups contained in (B) the specific curing agent to the number of equivalents of epoxy groups contained in (A) the epoxy resin (number of equivalents of amino groups / epoxy group equivalent number) is preferably in the range of 0.6 to 1.4, more preferably in the range of 0.7 to 1.3, and in the range of 0.8 to 1.2 More preferred.

The content of the (B) specific curing agent in the encapsulating resin composition is not particularly limited. The content of the specific curing agent (B) is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of fluidity, insulation reliability, etc., and 10 parts by mass. More preferably, it is up to 50 parts by mass.

The encapsulating resin composition may contain (B) a curing agent other than the specific curing agent. Other curing agents include phenol-based curing agents, acid anhydride-based curing agents, imidazole-based curing agents, carboxylic acid dihydrazide-based curing agents, and the like.

(B) When using a curing agent other than the specific curing agent, the content of the other curing agent in the sealing resin composition is determined from the viewpoint of fluidity, insulation reliability, etc. (A) epoxy resin 100 It is preferably from 0.5 to 5.0 parts by mass, more preferably from 1.0 to 3.0 parts by mass.

(B) When using a curing agent other than the specific curing agent, the content of the other curing agent in the encapsulating resin composition is It is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 35% by mass, and even more preferably 8% by mass to 20% by mass.

<(C) Resin having a phenoxy structure (phenoxy resin)>
The encapsulating resin composition of the present disclosure includes (C) a resin having a phenoxy structure (hereinafter also referred to as “(C) phenoxy resin”). (C) The encapsulating resin composition containing the phenoxy resin has the effect of suppressing the occurrence of the bleeding phenomenon, has excellent heat resistance and excellent moisture resistance, and tends to contribute to improving reliability after package encapsulation. It is in.
In the present disclosure, the “phenoxy structure” means a structure in which an oxygen atom is bonded to a benzene ring, and not only the phenoxy group (C ₆ H ₅ —O—) but also a part of the phenoxy group is substituted. and those obtained by partially reacting the phenoxy groups by hydrogenation or the like.

(C) The phenoxy resin can be used in liquid or solid form at 25°C. (C) When the phenoxy resin is liquid, it tends to be easily dissolved in the encapsulating resin composition. On the other hand, when the (C) phenoxy resin is solid, the encapsulating resin composition tends to be uniform by dissolving the (C) phenoxy resin in at least one of (A) the epoxy resin and (B) the specific curing agent. , tends to provide stable characteristics. (C) The phenoxy resin preferably contains a phenoxy resin that is liquid at 25°C, which tends to improve the fluidity of the encapsulating resin composition.

The (C) phenoxy resin in the encapsulating resin composition can be detected by a method such as gel permeation chromatography, pyrolysis gas chromatography, or infrared spectroscopy.

(C) The phenoxy resin is not particularly limited as long as it has a phenoxy structure in its molecular structure. (C) The phenoxy resin preferably has at least one of an epoxy group and a hydroxyl group in its skeleton. (C) Examples of phenoxy resins include phenoxy resins having a bisphenol skeleton, phenoxy resins having a novolak skeleton, phenoxy resins having a naphthalene skeleton, and phenoxy resins having a biphenyl skeleton. The bisphenol structure in the phenoxy resin having a bisphenol skeleton includes a bisphenol A structure, a bisphenol F structure, a bisphenol S structure, a brominated bisphenol A structure, a hydrogenated bisphenol A structure, and the like. The phenoxy resin may have an epoxy group, and in this case, the epoxy equivalent of the phenoxy resin may be more than 250 g/eq, may be 1000 g/eq or more, and may be 3,000 g/eq or more. may be
For resins having a phenoxy structure and an epoxy group, when the epoxy equivalent is 250 eq or less, it shall be included in (A) epoxy resin, and when the epoxy equivalent is more than 250 eq, it shall be included in (C) phenoxy resin. .

(C) The phenoxy resin is selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, and copolymerized epoxy resin of bisphenol F type and bisphenol A type from the viewpoint of cost, fluidity and heat resistance. It preferably contains at least one of the following, and more preferably contains a compound represented by the following general formula (1).

In general formula (1), A represents a structure represented by general formula (2), and terminal group B represents a hydroxyl group or a group represented by general formula (3). In general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group. n represents an integer from 1 to 1,000. When n is an integer of 2 or more, two or more A's may be the same or different. The two terminal groups B may be the same or different.

(C) The weight-average molecular weight (M _w ) of the phenoxy resin is preferably 500 or more, more preferably 2,000 or more, from the viewpoint of more suitably suppressing bleeding. Moreover, _Mw is preferably 5,000 or more from the viewpoint of heat resistance, and more preferably 20,000 or more from the viewpoint of further suitably suppressing bleeding. _Mw is preferably 100,000 or less from the viewpoint of fluidity.

(C) As a phenoxy resin, you may use a commercial item. Commercially available (C) phenoxy resins include jER1256, jER4250, jER4275 manufactured by Mitsubishi Chemical Corporation, YP-50 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., YP-50S, YP-70, ZX-1356-2, FX- 316, YPB-43C, YPB-43M and the like. (C) The phenoxy resin is not limited to these specific examples. (C) A phenoxy resin may be used individually by 1 type, or may use 2 or more types together.

The content of (C) the phenoxy resin in the encapsulating resin composition is not particularly limited. (C) The content of the phenoxy resin is 0.1 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of suitably suppressing the occurrence of bleeding while maintaining high fluidity and high heat resistance. It is preferably 15 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, and even more preferably 1.5 parts by mass to 6 parts by mass.

The content of (C) the phenoxy resin in the encapsulating resin composition is not particularly limited as long as the effect of suppressing the occurrence of the bleeding phenomenon is obtained. For example, from the viewpoint of heat resistance, the content of (C) the phenoxy resin is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, relative to the encapsulating resin composition. more preferred. In addition, the content of (C) the phenoxy resin is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, relative to the sealing resin composition from the viewpoint of fluidity. More preferably, it is 0.05% by mass to 1.0% by mass. In addition, the content of (C) the phenoxy resin is 0.05 mass with respect to the encapsulating resin composition from the viewpoint of suitably suppressing the occurrence of the bleeding phenomenon while maintaining high fluidity and high heat resistance. % to 2.0% by mass, more preferably 0.1% to 1.5% by mass, even more preferably 0.3% to 1.2% by mass.
(C) The higher the content and content of the phenoxy resin, the greater the effect of suppressing the occurrence of the bleeding phenomenon. It tends to be possible to suppress the decline.

<(D) Inorganic filler>
The encapsulating resin composition of the present disclosure contains (D) an inorganic filler.
(D) A cured product of a sealing resin composition containing an inorganic filler tends to be excellent in heat cycle resistance, moisture resistance, and stress reduction.

(D) The inorganic filler is not particularly limited. Specific examples of the inorganic filler (D) include silica such as colloidal silica, hydrophobic silica, and spherical silica, and talc, with spherical silica being preferred from the viewpoint of fluidity during coating.

In the present disclosure, silica being “spherical” is as follows.
First, when natural silica or synthetic silica is heat-treated to be spherical, particles that are not completely melted may not be perfectly spherical. In addition, a plurality of fused particles may coexist. Furthermore, the evaporated silica vapor adheres to the surface of other particles and solidifies, and as a result, spherical silica particles to which fine particles are adhered may be obtained. The fact that silica is substantially spherical means that particles having such a shape can be mixed. The diameter of the smallest circle circumscribing the projected image of )], when particles with this value of 0.9 or more account for 90% by mass or more of the inorganic filler silica as a whole, silica is considered to be “spherical” We will call it.

As the inorganic filler (D), from the viewpoint of fluidity, spherical silica having an average particle size of 0.01 μm to 20 μm is preferable, and spherical silica having an average particle size of 0.02 μm to 10 μm is more preferable.
A method for measuring the average particle size in the present disclosure is described below.
The average particle size is a value measured from the particle size distribution based on the number of particles and their frequency using a laser diffraction/scattering particle size distribution analyzer LA-920 (manufactured by HORIBA, Ltd.). As the dispersing solvent, it is preferable to use either water, acetone or ethanol to disperse the particles. As the measurement conditions, the particle concentration is set to several tens ppm to several hundred ppm based on mass, the ultrasonic treatment time is set to 30 minutes, and the measurement temperature is set to room temperature (25° C.).

Moreover, the specific surface area of (D) the inorganic filler is not particularly limited. Among them, from the viewpoint of fluidity and reliability, the specific surface area of the inorganic filler (D) is preferably 0.3 mm ² /g to 300 ^{mm 2} /g, and more preferably 1.0 mm ² /g to 100 mm ² /g. It is more preferable to have The specific surface area of the (D) inorganic filler is measured from the nitrogen adsorption capacity at 77K according to JIS Z 8830.

(D) As an inorganic filler, you may use a commercial item. Commercially available inorganic fillers (D) include spherical silica manufactured by Admatechs Co., Ltd. (product names: SO-E2, SE2300, SE2200-SEJ, etc.). (D) The inorganic filler is not limited to these specific examples. (D) Inorganic fillers may be used singly or in combination of two or more.

(D) The inorganic filler may be previously surface-treated with at least one of the following (F) coupling agents. An inorganic filler and (D) an inorganic filler that is not surface-treated may be used in combination. (F) By using the (D) inorganic filler surface-treated with a coupling agent, the affinity between the (D) inorganic filler and the resin component is improved, and the workability of the sealing resin composition and fluidity, as well as toughness, elastic modulus and adhesive strength of the cured product.

(D) When the inorganic filler is surface-treated with the (F) coupling agent, the ratio of the (D) inorganic filler and the (F) coupling agent is the (F) cup with respect to the (D) inorganic filler. The ring agent is preferably 0.2% by mass to 5.0% by mass, more preferably 0.3% by mass to 3.0% by mass, and 0.4% by mass to 2.0% by mass. It is even more preferable to have

The content of the inorganic filler (D) is preferably 5 parts by mass to 80 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of fluidity, insulation reliability, etc., and 20 parts by mass. More preferably, it is up to 70 parts by mass.

(D) The content of the inorganic filler is preferably 40% by mass to 85% by mass, and 50% by mass to 75% by mass, relative to the resin composition for sealing, from the viewpoint of fluidity, insulation reliability, etc. It is more preferably 55% by mass to 70% by mass.

When the sealing resin composition contains (F) an inorganic filler previously surface-treated with a coupling agent (D), the (F) surface-treated with a coupling agent (D) The content of the inorganic filler is preferably 5 parts by mass to 80 parts by mass, more preferably 20 parts by mass to 70 parts by mass, with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of fluidity, adhesiveness, etc. is more preferable.

When the encapsulating resin composition contains (F) an inorganic filler previously surface-treated with a coupling agent (D), its content is It is preferably 40% by mass to 85% by mass, more preferably 50% by mass to 75% by mass, even more preferably 55% by mass to 70% by mass, relative to the resin composition for use.

<(E) Rubber Additive>
The encapsulating resin composition of the present disclosure may optionally contain (E) a rubber additive.
(E) A cured product of a sealing resin composition containing a rubber additive tends to be excellent in stress relaxation.

(E) The type of rubber additive is not particularly limited, and can be appropriately selected from conventionally known ones. (E) Specific examples of the rubber additive include acrylic rubber, urethane rubber, silicone rubber, and butadiene rubber. (E) The rubber additive may be liquid at 25°C or solid at 25°C.

When the (E) rubber additive is solid at 25° C., the form of the (E) rubber additive is not particularly limited, and may be particulate, powder, pellet, or the like. From the viewpoint of heat resistance, the (E) rubber additive is preferably particulate. (E) When the rubber additive is particulate, the average particle size of the (E) rubber additive is preferably 0.01 μm to 20 μm, more preferably 0.02 μm to 10 μm, and more preferably 0.03 μm to 5 μm is even more preferable.

When the (E) rubber additive is liquid at 25° C., the (E) rubber additive includes low molecular weight components such as polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, polypropylene oxide, and polydiorganosiloxane. The weight average molecular weight of the low molecular weight component is preferably 5,000 to 80,000, more preferably 8,000 to 50,000.

When the (E) rubber additive is solid at 25° C., it is preferably used after heating to dissolve it in (A) the epoxy resin or (B) the specific curing agent. In addition, (E) the rubber additive may have a group that reacts with an epoxy group at its end. The (E) rubber additive having a group that reacts with an epoxy group at its end can be liquid at 25°C or solid at 25°C. A carboxy group, a hydroxyl group, an amino group, etc. are mentioned as a group which reacts with an epoxy group.

(E) As the rubber additive, a commercially available product may be used. Commercially available (E) rubber additives include CTBN1300, ATBN1300-16, CTBN1008-SP manufactured by Ube Industries, Ltd., silicone rubber powder manufactured by Dow Corning Toray Co., Ltd. (product name: AY42-119), manufactured by JSR Corporation. rubber powder (product name: XER81) and the like. (E) Rubber additives are not limited to these specific examples. (E) Rubber additives may be used alone or in combination of two or more.

When the encapsulating resin composition contains (E) a rubber additive, the content of (E) rubber additive is, from the viewpoint of fluidity, adhesion, etc., relative to 100 parts by mass of (A) epoxy resin , preferably 0.2 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass.

When the encapsulating resin composition contains the (E) rubber additive, the content of the (E) rubber additive is 0.00% relative to the encapsulating resin composition, from the viewpoint of fluidity, adhesion and the like. 05% by mass to 5.0% by mass, more preferably 0.1% by mass to 4.0% by mass, even more preferably 0.4% by mass to 3.0% by mass. .

<(F) Coupling agent>
The encapsulating resin composition may contain (F) a coupling agent, if necessary.
(F) A sealing resin composition containing a coupling agent tends to have excellent adhesion.

(F) The type of the coupling agent is not particularly limited, and can be appropriately selected from those conventionally known. (F) Specific examples of the coupling agent include silane compounds having at least one selected from the group consisting of primary amino groups, secondary amino groups and tertiary amino groups, silane compounds having an epoxy group, and mercapto groups. silane compounds having an alkyl group, silane compounds having a phenyl group, silane compounds having a ureido group, silane compounds having a methacryl group, silane compounds having an acrylic group, and silane compounds having a vinyl group. ; and titanate-based compounds. Among these, a silane compound having an epoxy group is preferable from the viewpoint of adhesion of the encapsulating resin composition.

(F) As the coupling agent, a commercially available product may be used. Commercially available coupling agents (F) include Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-402, KBM-403, KBE-403, KBE-903, KBE-9103, KBM-573, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-1003, KBE-585, KBM-9659, KBM-803, KBE-846, KBE-9007, X-12-967C, KBM-103, Examples include KBM-202SS. (F) The coupling agent is not limited to these specific examples. (F) Coupling agents may be used alone or in combination of two or more.

(F) The coupling agent may be contained in the encapsulating resin composition in a state of adhering to the surface of the (D) inorganic filler as a surface treatment agent for the (D) inorganic filler.

When the encapsulating resin composition contains (F) a coupling agent, the content of the (F) coupling agent is, from the viewpoint of fluidity, heat resistance, etc., relative to 100 parts by mass of the (A) epoxy resin, It is preferably from 0.2 parts by mass to 5.0 parts by mass, more preferably from 0.5 parts by mass to 3.0 parts by mass.

When the encapsulating resin composition contains (F) the coupling agent, the content of the (F) coupling agent is 0.00% relative to the encapsulating resin composition, from the viewpoint of fluidity, heat resistance, and the like. 05% by mass to 5% by mass, more preferably 0.1% by mass to 4.0% by mass, even more preferably 0.4% by mass to 3.0% by mass.

<Other ingredients>
The encapsulating resin composition contains, if necessary, a thixotropic agent for improving workability, a pigment such as carbon black, a dye, an ion trapper, and a neutralizing agent, as long as the effect of suppressing the occurrence of the bleeding phenomenon can be obtained. Foaming agents, leveling agents, antioxidants, curing accelerators, reactive diluents, organic solvents and the like may also be included.

<Method for preparing encapsulating resin composition>
The encapsulating resin composition of the present disclosure includes (A) an epoxy resin, (B) a specific curing agent, (C) a phenoxy resin and (D) an inorganic filler, (E) a rubber additive, and (F) a coupling It can be obtained by stirring, melting, mixing, dispersing, etc., all together or separately the other additives such as agents, while applying heat treatment if necessary. In particular, when (A) epoxy resin, (B) specific curing agent, (C) phenoxy resin, etc. are solid, if they are mixed in solid form, the viscosity increases and workability may decrease. It is preferable to liquefy by and mix. Apparatuses for mixing, stirring, dispersing, etc. are not particularly limited, and examples include a laikai machine equipped with a stirring device, a heating device, etc., a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like. By using these devices, the above components are mixed, kneaded, and defoamed as necessary to obtain the encapsulating resin composition.

<Physical properties of encapsulating resin composition>
The viscosity of the encapsulating resin composition is not particularly limited. Among them, from the viewpoint of fluidity, the viscosity of the encapsulating resin composition is preferably 0.1 Pa·s to 100.0 Pa·s at 25°C, and preferably 0.1 Pa·s to 50.0 Pa·s at 25°C. s is more preferred. The viscosity of the encapsulating resin composition at 25° C. can be measured using an E-type viscometer (cone angle 3°, number of revolutions 10 rpm).

When the sealing resin composition is used as an underfill material for flip chips, etc., the sealing resin composition is used as an index when filling a narrow gap of several tens of μm to several hundreds of μm at around 100 ° C. to 120 ° C. The viscosity of is preferably 0.40 Pa s or less at 110 ° C., more preferably 0.25 Pa s or less at 110 ° C., and even more preferably 0.15 Pa s or less at 110 ° C. , 0.12 Pa·s or less at 110°C, and more preferably 0.10 Pa·s or less at 110°C. The viscosity of the encapsulating resin composition at 110° C. is measured using a rheometer AR2000 (manufactured by TA Instruments Japan, aluminum cone 40 mm, shear rate 32.5/sec). can be done.

In the sealing resin composition, the ratio of the viscosity at a rotation speed of 2.5 rotations/minute and the viscosity at a rotation speed of 10 rotations/minute measured at 25 ° C. using an E-type viscometer [(rotation speed 2.5 The thixotropic index, which is the viscosity at revolutions/minute)/(viscosity at a number of revolutions of 10 revolutions/minute), is preferably 0.5 to 1.5, and preferably 0.8 to 1.2. is more preferred. When the thixotropic index is within the above range, fillet formability tends to be further improved when the encapsulating resin composition is used as an underfill material. The viscosity and thixotropic index of the encapsulating resin composition can be set within desired ranges by appropriately selecting the composition ratio of each component.

The pot life, which is an index of the storage stability of the encapsulating resin composition, is the rate of change in viscosity before and after storage in an atmosphere of 25° C. for 24 hours, and is calculated using the following formula.
Pot life (%) = 100 × [(viscosity after storage - viscosity before storage) / viscosity before storage]

A smaller pot life value indicates higher storage stability, and is preferably 150% or less, more preferably 130% or less, and even more preferably 100% or less.

[Cured product]
The cured product of the present disclosure is obtained by curing a sealing resin composition capable of suppressing the occurrence of the bleeding phenomenon. The cured product can be produced by curing the encapsulating resin composition by, for example, performing a heat treatment at 80° C. to 165° C. for 1 minute to 150 minutes. It is used as a sealing material for stopping.

[Electronic parts equipment]
An electronic component device of the present disclosure includes a substrate having a circuit layer, an electronic component disposed on the substrate and electrically connected to the circuit layer, and a book disposed in a gap between the substrate and the electronic component. and a cured product of the disclosure. The electronic component device of the present disclosure can be obtained by encapsulating an electronic component with the encapsulating resin composition of the present disclosure. Since the electronic component is encapsulated with the encapsulating resin composition of the present disclosure, the electronic component device of the present disclosure has excellent temperature cycle resistance.

As electronic component devices, semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, etc. , resistors, resistor arrays, coils, and passive elements such as switches are mounted, and electronic component devices obtained by encapsulating necessary portions with the encapsulating resin composition of the present disclosure.
In particular, one of the objects to which the present disclosure can be applied is a semiconductor device in which a semiconductor element is flip-chip bonded to wiring formed on a rigid wiring board, a flexible wiring board, or glass by bump connection. Specific examples include electronic component devices such as flip chip BGA (Ball Grid Array), LGA (Land Grid Array), and COF (Chip On Film).

The encapsulating resin composition of the present disclosure is suitable as an underfill material for flip chips with excellent reliability. In the field of flip chips, to which the encapsulating resin composition of the present disclosure is particularly preferably applied, the bump material connecting the wiring board and the semiconductor element is not the conventional lead-containing solder, but Sn--Ag--Cu or the like. It is a flip-chip semiconductor component using lead-free solder. The encapsulating resin composition of the present disclosure can maintain good reliability even for a flip chip that is bump-connected using lead-free solder, which is physically brittle compared to conventional lead solder. In addition, reliability can be improved by applying the sealing resin composition of the present disclosure when mounting a chip scale package such as a wafer level CSP on a substrate.

[Manufacturing method of electronic component device]
The manufacturing method of the electronic component device of the present disclosure includes a substrate having a circuit layer, and an electronic component disposed on the substrate and electrically connected to the circuit layer, and the sealing resin composition of the present disclosure. It has a step of sealing using.
There is no particular limitation on the step of sealing a substrate having a circuit layer and an electronic component using the sealing resin composition of the present disclosure. For example, after connecting an electronic component and a substrate having a circuit layer, a sealing resin composition is applied to the gap between the electronic component and the substrate using capillary action, and then a curing reaction of the sealing resin composition. and applying the sealing resin composition of the present disclosure to the surface of at least one of the substrate and the electronic component having the circuit layer first, and connecting the electronic component to the substrate by thermocompression bonding. and a pre-coating method in which the connection of the electronic component and the substrate and the curing reaction of the encapsulating resin composition are performed collectively.
Examples of methods for applying the encapsulating resin composition include a casting method, a dispensing method, and a printing method.

The curing conditions for curing the sealing resin composition applied to the gap between the electronic component and the substrate are not particularly limited, for example, heat treatment at 80 ° C. to 165 ° C. for 1 minute to 150 minutes. is preferred.

By using the encapsulating resin composition of the present disclosure, it is possible to easily produce an electronic component device such as a flip-chip mounted body in which the bleeding phenomenon is suppressed.

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited to the following examples. In the following examples, parts and % represent parts by weight and % by weight unless otherwise specified.

(Examples 1 to 14, Comparative Example 1)
Each component was blended so as to have the composition shown in Tables 1 and 2, and kneaded and dispersed using a triple roll and a vacuum lykai machine to prepare encapsulating resin compositions of Examples 1 to 14 and Comparative Example 1. bottom. The unit of formulation in the table is parts by mass, and "-" indicates "no formulation". Furthermore, the content (% by mass) of the inorganic filler in the encapsulating resin composition was calculated from the blending amount of each component.

(A) As the epoxy resin, the following materials were prepared.
Epoxy resin 1: amine-type epoxy resin having a trifunctional epoxy group (manufactured by Mitsubishi Chemical Corporation, trade name “jER-630”, epoxy equivalent of 96 g / eq, weight average molecular weight of 290)
・ Epoxy resin 2: bisphenol F type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name “YDF-8170C”, epoxy equivalent of 160 g / eq, weight average molecular weight of 350)

(B) The following materials were prepared as the specific curing agent.
- Amine curing agent 1: diaminotoluene type amine curing agent (manufactured by Mitsubishi Chemical Corporation, trade name "jER Cure W")
- Amine curing agent 2: diaminophenylmethane type amine curing agent (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayahard-AA")

(C) As the phenoxy resin, the following materials were prepared.
Phenoxy resin 1: phenoxy resin having a bisphenol A structure ((manufactured by Mitsubishi Chemical Corporation, trade name "1001", weight average molecular weight of 900)
- Phenoxy resin 2: phenoxy resin having a bisphenol A structure (manufactured by Mitsubishi Chemical Corporation, trade name "1007", weight average molecular weight of 2,900)
- Phenoxy resin 3: phenoxy resin having a bisphenol A structure (manufactured by Mitsubishi Chemical Corporation, trade name "1010", weight average molecular weight of 5,500)
- Phenoxy resin 4: phenoxy resin having a bisphenol A structure (manufactured by Mitsubishi Chemical Corporation, trade name "1256", weight average molecular weight of 50,000)
Phenoxy resin 5: Phenoxy resin having a bisphenol F type structure (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name “ZX-1356-2”, weight average molecular weight of 50,000)

(D) As an inorganic filler, the following materials were prepared.
・ Inorganic filler 1: Spherical silica treated with a silane compound having an epoxy group with an average particle size of 0.5 μm (manufactured by Admatechs Co., Ltd., trade name “SE2200-SEJ”)

Carbon black (manufactured by Mitsubishi Chemical Corporation, trade name “MA-100”) was prepared as a coloring agent.

Various properties of the encapsulating resin composition obtained using the above materials were evaluated as follows. Further, Tables 1 and 2 below show respective numerical values.

(1) Fluidity: Viscosity and Thixotropic Index was used and measured with a sample volume of 2.5 mL. In addition, the thixotropic index at 25° C. is the ratio of the viscosity at a rotation speed of 2.5 rotations/minute to the viscosity at a rotation speed of 10 rotations/minute [(viscosity at a rotation speed of 2.5 rotations/minute)/(rotation speed Viscosity at 10 rpm)].
The viscosity (Pa·s) at 110° C. was measured using a rheometer AR2000 (aluminum cone 40 mm, shear rate 32.5/sec) with a sample volume of 0.7 mL.

(2) Heat resistance: glass transition temperature (Tg) and coefficient of thermal expansion (CTE)
The encapsulating resin composition was cured at 150° C. for 120 minutes to prepare a test piece (φ4 mm×20 mm). For the prepared test piece, using a thermomechanical analyzer (manufactured by TA Instruments Japan Co., Ltd., trade name TMAQ400), a load of 15 g, a measurement temperature of -50 ° C. to 220 ° C., and a heating rate of 5 ° C./min. The glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) were measured under the conditions of
CTE1 is the coefficient of thermal expansion in the temperature range below Tg, and CTE2 is the coefficient of thermal expansion in the temperature range above Tg. Tg and CTE indicate thermal stability, Tg is preferably about 100° C. to 130° C., and CTE1 and CTE2 are preferably as low as possible.

(3) Measurement of bleed length The solder resist substrate was subjected to Ar ₂ plasma treatment (400 W, 2 minutes), and the sealing resin composition filled in a syringe was placed on the solder resist substrate subjected to the Ar ₂ plasma treatment. The material was potted at 30 mg with a 25G needle and cured at 150° C. for 120 minutes. After curing, the bleed length was measured using an optical microscope. Solder resist 1 (PSR-4000-AUS308 manufactured by Taiyo Ink Mfg. Co., Ltd.) and solder resist 2 (PSR manufactured by Taiyo Ink Mfg. Co., Ltd.) are applied to the substrate on FR-4 (manufactured by Hitachi Chemical Co., Ltd., MRC-E-679). -4000-AUS703) were used respectively. The shorter the bleed length on both substrates, the better.

From the results in Tables 1 and 2, the encapsulating resin compositions of Examples 1 to 14 were excellent in heat resistance and fluidity, and the bleeding was shorter than that of the encapsulating resin composition of Comparative Example 1. From this, it was found that the encapsulating resin composition of this example can suppress the occurrence of the bleeding phenomenon while maintaining high heat resistance and high fluidity.

All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually noted to be incorporated by reference. incorporated herein by reference.

Claims (9)

(A) an epoxy resin, (B) a curing agent having at least one amino group, (C) a resin having a phenoxy structure and (D) an inorganic filler,
(A) the epoxy resin includes an amine type epoxy resin and a bisphenol F type epoxy resin having a trifunctional epoxy group,
Regarding the resin having a phenoxy structure and an epoxy group, when the epoxy equivalent is 250 g/eq or less, it corresponds to the above (A) epoxy resin, and when the epoxy equivalent is more than 250 g/eq, it has the above (C) phenoxy structure. corresponds to resin,
A sealing resin composition having a viscosity of 0.40 Pa s or less at 110° C. (provided that the alkenyl group of the phenol resin and the number of silicon atoms in one molecule represented by the following average composition formula (3) are 20 to 400 and obtained by an addition reaction with the SiH group of an organopolysiloxane having 1 to 5 hydrogen atoms (SiH groups) bonded to silicon atoms, and represented by the following structural formula (4): Excludes encapsulating resin compositions involving coalescence.
H _a R ² _b SiO _(4-ab) (3)).

(In the above formula (3), R ² is a substituted or unsubstituted monovalent hydrocarbon group, a is 0.01 to 0.1, b is 1.8 to 2.2, 1.81 ≤ a + b ≤ 2 .3.
In the above formula (4), R ² is a substituted or unsubstituted monovalent hydrocarbon group, R ³ is -CH ₂ CH ₂ CH ₂ -, -OCH ₂ -CH(OH)-CH ₂ -O- CH ₂ CH ₂ CH ₂ — or —O—CH ₂ CH ₂ CH ₂ —, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is an integer of 4-199, p is an integer of 1-10, and q is an integer of 1-10. ) 2. The encapsulating resin composition according to claim 1, wherein (C) the resin having a phenoxy structure has a weight average molecular weight ( _Mw ) of 500 or more and 100,000 or less. 2. The encapsulating resin composition according to claim 1, wherein (C) the resin having a phenoxy structure has a weight average molecular weight ( _Mw ) of 2,000 or more and 100,000 or less. The encapsulating resin composition according to any one of claims 1 to 3, wherein (C) the resin having a phenoxy structure contains a compound represented by the following general formula (1).

(In the general formula (1), A represents a structure represented by the general formula (2), and the terminal group B represents a hydroxyl group or a group represented by the general formula (3). In the general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, n represents an integer of 1 to 1000. When n is an integer of 2 or more, two or more A may be the same or different. The two terminal groups B may be the same or different.) 5. The content of (C) the resin having a phenoxy structure is 0.05% by mass to 2.0% by mass relative to the encapsulating resin composition, according to any one of claims 1 to 4. The encapsulating resin composition. The encapsulating resin composition according to any one of claims 1 to 5, which is used for encapsulating electronic component devices. A cured product obtained by curing the encapsulating resin composition according to any one of claims 1 to 6. a substrate having a circuit layer;
an electronic component disposed on the substrate and electrically connected to the circuit layer;
The cured product according to claim 7 arranged in the gap between the substrate and the electronic component;
An electronic component device comprising: The sealing resin composition according to any one of claims 1 to 6, wherein a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer are combined. A method of manufacturing an electronic component device, comprising a step of sealing using