JP7040129B2 - Encapsulating resin composition - Google Patents

Description

The present invention relates to a sealing resin composition. Furthermore, the present invention relates to a semiconductor chip package using a sealing resin composition.

In recent years, the demand for small high-performance electronic devices such as smartphones and tablet devices has increased, and along with this, the insulating materials used in these small electronic devices are also required to have higher functionality. As such an insulating material, for example, a material formed by curing a resin composition is known (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2017-82052

In recent years, smaller semiconductor chip packages have been demanded, and due to the miniaturization of semiconductor chip packages, even in the sealing layer for encapsulating semiconductor chips, the gaps between fine wiring and bumps are filled without voids and gaps. Fillability that enables filling is required. Further, the sealing layer and the insulating layer are required to have high adhesion even after being placed in a high temperature and high humidity for a long time. For example, an insulating layer in close contact with a silicon chip is required to be in high temperature and high humidity. It is required that it does not easily come off from the silicon chip even after being placed in the silicon for a long time. However, the conventional resin composition still has room for improvement in the evaluation of high filling property and adhesion.

The present invention has been devised in view of the above problems, and is a sealing resin capable of obtaining a cured product having excellent filling properties and high adhesion even after being placed in a high temperature and high humidity for a long time. It is an object of the present invention to provide a composition; and a semiconductor chip package containing a cured product of the sealing resin composition.

As a result of diligent studies to solve the above problems, the present inventor has prepared a resin composition for encapsulating a predetermined amount of (A) glycidylamine type epoxy resin and (B) the compound represented by the general formula (1). It was found that a sealing resin composition capable of obtaining a cured product having excellent filling properties and high adhesion even after being placed in a high temperature and high humidity for a long time can be obtained by containing the mixture in the above. The present invention has been completed. That is, the present invention includes the following.

（式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ独立に水素原子、又はメチル基を表し、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０は、それぞれ独立に水素原子、メチル基、又はヒドロキシル基を表す。）
［２］ （Ａ）成分が、２官能又は３官能のグリシジルアミン型エポキシ樹脂である、［１］に記載の封止用樹脂組成物。
［３］ 一般式（１）中、Ｒ^４～Ｒ^１０のうち少なくとも１つはヒドロキシル基を表す、［１］又は［２］に記載の封止用樹脂組成物。
［４］ 一般式（１）中、Ｒ^４～Ｒ^９は、それぞれ独立に水素原子、メチル基、又はヒドロキシル基を表し、Ｒ^１０は、ヒドロキシル基である、［３］に記載の封止用樹脂組成物。
［５］ 一般式（１）中、Ｒ^１～Ｒ^３のうち少なくとも１つはメチル基を表す、［１］～［４］のいずれかに記載の封止用樹脂組成物。
［６］ （Ｂ）成分が、下記式（２）で表される、［１］～［５］のいずれかに記載の封止用樹脂組成物。

［７］ （Ｂ）成分の含有量が、封止用樹脂組成物中の不揮発成分を１００質量％とした場合、０．５質量％以上５質量％以下である、［１］～［６］のいずれかに記載の封止用樹脂組成物。
［８］ （Ｃ）成分の含有量が、封止用樹脂組成物中の不揮発成分を１００質量％とした場合、８０質量％以上９５質量％以下である、［１］～［７］のいずれかに記載の封止用樹脂組成物。
［９］ （Ｃ）成分の平均粒径が、０．１μｍ以上１０μｍ以下である、［１］～［８］のいずれかに記載の封止用樹脂組成物。
［１０］ 液状の封止用樹脂組成物である、［１］～［９］のいずれかに記載の封止用樹脂組成物。
［１１］ 回路基板と、該回路基板に搭載された半導体チップと、前記半導体チップを封止する［１］～［１０］のいずれかに記載の封止用樹脂組成物の硬化物とを含む、半導体チップパッケージ。
［１２］ 半導体チップと、前記半導体チップを封止する［１］～［１０］のいずれかに記載の封止用樹脂組成物の硬化物とを含む、半導体チップパッケージ。 [1] (A) Glycidylamine type epoxy resin,
A sealing resin composition containing (B) a compound represented by the following general formula (1) and (C) an inorganic filler.
When the non-volatile component in the sealing resin composition is 100% by mass, the content of the component (A) is 3% by mass or more and 15% by mass or less.

(In formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R, respectively. ¹⁰ independently represents a hydrogen atom, a methyl group, or a hydroxyl group.)
[2] The sealing resin composition according to [1], wherein the component (A) is a bifunctional or trifunctional glycidylamine type epoxy resin.
[3] The sealing resin composition according to [1] or [2], wherein at least one of R ⁴ to R ¹⁰ in the general formula (1) represents a hydroxyl group.
[4] In the general formula (1), R ⁴ to R ⁹ independently represent a hydrogen atom, a methyl group, or a hydroxyl group, and R ¹⁰ is a hydroxyl group, respectively, for sealing according to [3]. Resin composition.
[5] The sealing resin composition according to any one of [1] to [4], wherein at least one of R ¹ to R ³ in the general formula (1) represents a methyl group.
[6] The sealing resin composition according to any one of [1] to [5], wherein the component (B) is represented by the following formula (2).

[7] The content of the component (B) is 0.5% by mass or more and 5% by mass or less when the non-volatile component in the sealing resin composition is 100% by mass, [1] to [6]. The sealing resin composition according to any one of.
[8] Any of [1] to [7], wherein the content of the component (C) is 80% by mass or more and 95% by mass or less when the non-volatile component in the sealing resin composition is 100% by mass. The sealing resin composition described in Crab.
[9] The sealing resin composition according to any one of [1] to [8], wherein the average particle size of the component (C) is 0.1 μm or more and 10 μm or less.
[10] The sealing resin composition according to any one of [1] to [9], which is a liquid sealing resin composition.
[11] A circuit board, a semiconductor chip mounted on the circuit board, and a cured product of the sealing resin composition according to any one of [1] to [10] for sealing the semiconductor chip are included. , Semiconductor chip package.
[12] A semiconductor chip package comprising a semiconductor chip and a cured product of the sealing resin composition according to any one of [1] to [10] for encapsulating the semiconductor chip.

According to the present invention, a sealing resin composition capable of obtaining a cured product having excellent filling property and high adhesion even after being left in a high temperature and high humidity for a long time, and the above-mentioned sealing resin. A semiconductor chip package containing a cured product of the composition can be provided.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof. In the present invention, the content of each component in the sealing resin composition is a value when the non-volatile component in the sealing resin composition is 100% by mass, unless otherwise specified.

[Plastic composition for encapsulation]
The sealing resin composition of the present invention contains (A) a glycidylamine type epoxy resin, (B) a compound represented by the general formula (1), and (C) an inorganic filler. In the composition, when the non-volatile component in the sealing resin composition is 100% by mass, the content of the component (A) is 3% by mass or more and 15% by mass or less. The content of the (A) glycidylamine type epoxy resin, (B) the compound represented by the general formula (1), and (C) the inorganic filler in combination, and (A) the glycidylamine type epoxy resin is contained. The desired range of the present invention is that the sealing resin composition has excellent filling property and a cured product having adhesiveness can be obtained even after being placed in a high temperature and high humidity for a long time. The effect of can be obtained. The cured product of this sealing resin composition can be preferably used as an insulating layer and a sealing material of a semiconductor chip package, and particularly preferably as a sealing material, by taking advantage of its excellent properties.

Further, the sealing resin composition may be further combined with an arbitrary component in combination with (A) a glycidylamine type epoxy resin, (B) a compound represented by the general formula (1), and (C) an inorganic filler. May include. Examples of the optional component include (D) epoxy resin, (E) curing agent, and the like. Hereinafter, each component contained in the sealing resin composition will be described.

<(A) Glycidylamine type epoxy resin>
The sealing resin composition contains a glycidylamine type epoxy resin as the component (A), and the content of the (A) glycidylamine type epoxy resin is 100% by mass of the non-volatile component in the sealing resin composition. If it is, it is 3% by mass or more and 15% by mass or less. By containing a predetermined amount of the (A) glycidylamine type epoxy resin in the sealing resin composition, the viscosity of the sealing resin composition can be lowered, and the cured product of the sealing resin composition can be reduced. It is also possible to improve the heat resistance of the plastic.

As the (A) glycidylamine type epoxy resin, an epoxy resin in which a glycidyl group is directly bonded to a nitrogen atom can be used. Above all, from the viewpoint of further lowering the viscosity and further improving the heat resistance of the cured product, a bifunctional or trifunctional glycidylamine type epoxy resin is preferable, and a trifunctional glycidylamine type epoxy resin is more preferable. preferable. (A) The glycidylamine type epoxy resin may be used in combination with a bifunctional glycidylamine type epoxy resin and a trifunctional glycidylamine type epoxy resin. For example, the trifunctional glycidylamine type epoxy resin represents a glycidylamine type epoxy resin having three epoxy groups in the molecule.

The (A) glycidylamine type epoxy resin is preferably an aromatic glycidylamine type epoxy resin having an aromatic ring in the molecule from the viewpoint of further improving heat resistance and lowering the coefficient of linear thermal expansion.

（式（Ａ）中、Ｒ^１１は、それぞれ独立にグリシジルエーテル基、又は炭素原子数１～６のアルキル基を表し、Ｒ^１２は水素原子、又は炭素原子数１～１０の１～３価の炭化水素基を表す。ｎはそれぞれ独立に０～４の整数を表し、ｍは１～３の整数を表す。） The glycidylamine type epoxy resin (A) is preferably represented by the following formula (A).

(In the formula (A), R ¹¹ independently represents a glycidyl ether group or an alkyl group having 1 to 6 carbon atoms, and R ¹² is a hydrogen atom or a 1 to 3 valence having 1 to 10 carbon atoms. Represents a hydrocarbon group. N independently represents an integer of 0 to 4, and m represents an integer of 1 to 3.)

R ¹¹ independently represents a glycidyl ether group or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. The alkyl group having 1 to 6 carbon atoms is preferably bonded to the ortho position with reference to the binding site between the nitrogen atom and the aromatic ring. Above all, from the viewpoint of obtaining the desired effect of the present invention, the glycidyl ether group is preferable as R11, and the glycidyl ether group is preferably bonded to the para position based ^on the binding site between the nitrogen atom and the aromatic ring. ..

R ¹² represents a hydrogen atom or a 1 to 3 valent hydrocarbon group having 1 to 10 carbon atoms. Hydrocarbon groups having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, and a trivalent group derived from an alkyl group having 1 to 10 carbon atoms. Examples thereof include an aryl group having 6 to 10 carbon atoms and an arylene group having 6 to 10 carbon atoms. As the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable. As the alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 5 carbon atoms is preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group. Among them, when m is 1, from the viewpoint of obtaining the desired effect of the present invention, R ¹² is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group. When m is 2, the R ¹² is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably a methylene group, from the viewpoint of obtaining the desired effect of the present invention.

n independently represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 1. m represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

(A) As the glycidylamine type epoxy resin, a commercially available product may be used, for example, "EP3980S" (diglycidyl-o-toluidine) manufactured by ADEKA, "EP3950S", "EP3950L" manufactured by Mitsubishi Chemical Corporation, and "630" manufactured by Mitsubishi Chemical Corporation. "(Triglycidyl-p-aminophenol)," 630LSD "," ELM-100 "," ELM-100H "," ELM-434 "," ELM-434L "manufactured by Sumitomo Chemical Corporation, and the like.

(A) One type of glycidylamine type epoxy resin may be used alone, or two or more types may be used in combination at any ratio.

The content of the glycidylamine type epoxy resin (A) is 3% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass when the non-volatile component in the sealing resin composition is 100% by mass. % Or more, 15% by mass or less, preferably 14.5% by mass or less, and more preferably 14% by mass or less. (A) By setting the content of the glycidylamine type epoxy resin within the above range, the viscosity can be lowered and the heat resistance of the cured product of the sealing resin composition can be improved. Further, by setting the content of (A) the glycidylamine type epoxy resin within the above range, it is possible to suppress cracks in the cured product.

The epoxy equivalent of the glycidylamine type epoxy resin (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product of the sealing resin composition becomes sufficient, and a sealing layer having a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the glycidylamine type epoxy resin (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, (A) the weight average molecular weight of the glycidylamine type epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<Compound represented by formula (1) in (B)>
The sealing resin composition contains the compound represented by the formula (1) as the component (B). The component (B) has a function of reacting with an epoxy resin such as the component (A) and the component (D) described later to accelerate the curing of the sealing resin composition. By containing the compound represented by the formula (1) in the sealing resin composition, an increase in the viscosity of the sealing resin composition is suppressed, and the filling property, that is, the compression mold moldability and the molding underfill property are excellent. It will be like. Further, usually, according to the sealing resin composition, the generation of flow marks can be suppressed.

By containing the compound represented by the formula (B) (1) in the sealing resin composition, excellent filling properties can be obtained. (B) In the molecule of the compound represented by the formula (1), a group containing a naphthalene ring is bonded to a nitrogen atom via a methylene group, and a large steric hindrance action acts. Therefore, the reactivity of the nitrogen atom is suppressed. Therefore, the reaction by the compound represented by the formula (B) (1) proceeds slowly. Therefore, the increase in viscosity of the sealing resin composition in the filling environment is suppressed, and it becomes possible to obtain a cured product having excellent filling properties. Further, since the compatibility between the components contained in the sealing resin composition is excellent, the generation of flow marks can be suppressed. Therefore, usually, by using the component (A) and the component (B) in combination, the generation of flow marks is suppressed, and the PCT test resistance, the compression mold moldability of the cured product, and the molding underfill property are improved. become.

（式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ独立に水素原子、又はメチル基を表し、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０は、それぞれ独立に水素原子、メチル基、又はヒドロキシル基を表す。）

(In formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R, respectively. ¹⁰ independently represents a hydrogen atom, a methyl group, or a hydroxyl group.)

R ¹ , R ² , and R ³ independently represent a hydrogen atom or a methyl group, respectively. At least one of R ¹ to R ³ preferably represents a methyl group, and more preferably R ³ is a methyl group. When R ³ is a methyl group, R ¹ and R ² are preferably hydrogen atoms.

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ independently represent a hydrogen atom, a methyl group, or a hydroxyl group, respectively. It is preferable that at least one of R ⁴ to R ¹⁰ represents a hydroxyl group, and it is more preferable that R ¹⁰ is a hydroxyl group. When R ¹⁰ is a hydroxyl group, R ⁴ to R ⁹ independently represent a hydrogen atom, a methyl group, or a hydroxyl group, and R ⁴ to R ⁹ are preferably hydrogen atoms.

Examples of the compound represented by the formula (1) in (B) include a compound represented by the following formula (2), 1- (2-methylimidazolylmethyl) -2-naphthol, and 1- (4-methylimidazolylmethyl). ) -2-Naphthol, 1- (5-methylimidazolylmethyl) -2-naphthol, 1- (2,4-dimethylimidazolylmethyl) -2-naphthol, 1- (2,4,5-trimethylimidazolylmethyl) Naphthol compounds such as -2-naphthol; 1- (imidazolylmethyl) -2,3-naphthalenediol, 1- (2-methylimidazolylmethyl) -2,3-naphthalenediol, 1- (2,4-dimethylimidazolylmethyl) ) -2,3-naphthalenediol, 1- (2-methylimidazolylmethyl) -2,6-naphthalenediol, 1- (2-methylimidazolylmethyl) -7-methyl-2,6-naphthalenediol, 1-( 2-Methylimidazolylmethyl) -7-methyl-2,3-naphthalenediol compounds such as naphtholenediol; etc., among others, are represented by the following formula (2) from the viewpoint of remarkably exerting the effect of the present invention. It is preferably a compound. (B) The compound represented by the formula (1) may be used alone or in combination of two or more at any ratio.

(B) The content of the compound represented by the formula (1) is excellent in compression mold moldability and molding underfill property, and from the viewpoint of obtaining a cured product capable of suppressing the generation of flow marks, a sealing resin composition. When the non-volatile component in the medium is 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and preferably 5% by mass or less. It is preferably 4% by mass or less, more preferably 3% by mass or less.

<(C) Inorganic filler>
The sealing resin composition contains an inorganic filler as the component (C). (C) By using the inorganic filler, the insulating performance of the cured product of the sealing resin composition can be improved.

(C) An inorganic compound is used as the material of the inorganic filler. Examples of the material of the inorganic filler (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Among these, silica or alumina is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (C) The inorganic filler may be used alone or in combination of two or more at any ratio.

Usually, (C) the inorganic filler is contained in the sealing resin composition in the form of particles. (C) The average particle size of the inorganic filler is preferably 0.1 μm or more, more preferably 0.2 μm or more, particularly preferably 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 1.0 μm or more. It is preferably 10 μm or less, more preferably 7.0 μm or less, and particularly preferably 5.0 μm or less. When the average particle size of the inorganic filler (C) is in the above range, the filling property of the inorganic filler in the sealing resin composition is enhanced, and the desired effect of the present invention can be remarkably obtained. can.

(C) The average particle size of particles such as an inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a laser diffraction / scattering type particle size distribution measuring device can be used to create a particle size distribution of particles on a volume basis, and the average particle size can be measured as the median diameter from the particle size distribution. As the measurement sample, particles dispersed in a solvent such as water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

Examples of the (C) inorganic filler as described above include "ST7030-20" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "MSS-6" and "AC-5V" manufactured by Ryumori Co., Ltd .; "AC-5V" manufactured by Nippon Steel & Sumikin Materials Co., Ltd. SP60-05 "," SP507-05 "; Admatex" YC100C "," YA050C "," YA050C-MJE "," YA010C "; Denka" UFP-30 "," SFP-130MC "," FB " -7SDC, "FB-5SDC", "FB-3SDC"; Tokuyama Corporation "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; Admatex "SC2500SQ", "SO" -C4 "," SO-C2 "," SO-C1 "," FE9 "and the like can be mentioned.

(C) The inorganic filler is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, (C) the moisture resistance and dispersibility of the inorganic filler can be enhanced. Further, it is possible to improve the compatibility with the resin component and improve the flow mark property. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and titanate. Examples thereof include a system-based coupling agent, and an aminosilane-based coupling agent is preferable from the viewpoint of further improving the flow mark property.

Commercially available surface treatment agents include, for example, "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (Phenyltrimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupling agent) and the like can be mentioned. Of these, a nitrogen atom-containing silane coupling agent is preferable, an aminosilane-based coupling agent containing a phenyl group is more preferable, and N-phenyl-3-aminoalkyltrimethoxysilane is even more preferable. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in combination at any ratio.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of (C) the inorganic filler. The amount of carbon per unit surface area of the (C) inorganic filler is preferably 0.02 mg / m ² or more, more preferably 0.1 mg / m ² or more, from the viewpoint of improving the dispersibility of the inorganic filler. Particularly preferably, it is 0.2 mg / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, and particularly preferably. Is 0.5 mg / m ² or less.

The amount of carbon per unit surface area of the (C) inorganic filler is determined after the surface-treated (C) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (hereinafter, may be abbreviated as “MEK”)). , Can be measured. Specifically, a sufficient amount of methyl ethyl ketone and the (C) inorganic filler surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Then, after removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the (C) inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

(C) The specific surface area of the inorganic filler is preferably 1 m ² / g or more, more preferably 1.5 m ² / g or more, and particularly preferably 2 m ² / g or more, from the viewpoint of further improving the effect of the present invention. be. The upper limit is not particularly limited, but is preferably 20 m ² / g or less, 10 m ² / g or less, or 5 m ² / g or less. The specific surface area of the inorganic filler can be measured by the BET method.

The amount of the (C) inorganic filler in the resin composition is preferably 80% by mass or more, more preferably 80.5% by mass or more, still more preferably 81, based on 100% by mass of the non-volatile component in the resin composition. It is 5% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, and further preferably 91% by mass or less. (C) When the amount of the inorganic filler is within the above range, the desired effect of the present invention can be remarkably obtained.

<(D) Epoxy resin>
The sealing resin composition may contain an epoxy resin as the component (D). However, (D) epoxy resin excludes those corresponding to (A) glycidylamine type epoxy resin.

Examples of the epoxy resin include glycidyl ester type epoxy resin, bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentadiene type. Epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, cresol novolac type epoxy resin , Biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, alicyclic epoxy resin having an ester skeleton, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type Examples thereof include an epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The sealing resin composition preferably contains, as the (D) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the (E) epoxy resin. % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

As the (D) epoxy resin, a liquid epoxy resin may be used, a solid epoxy resin may be used, or a liquid epoxy resin and a solid epoxy resin may be used in combination. Above all, from the viewpoint of reducing the viscosity of the sealing resin composition, it is preferable to use a liquid epoxy resin as the (D) epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Examples of the liquid epoxy resin include glycidyl ester type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, and alicyclic epoxy resin having an ester skeleton. , Cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, aliphatic epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin and an alicyclic epoxy resin having an ester skeleton are more preferable.

Specific examples of the liquid epoxy resin include "JER871" and "JER872" manufactured by Mitsubishi Chemical Co., Ltd., "YD-171" (glycidyl ester type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; and "HP4032" manufactured by DIC Co., Ltd. "HP4032D", "HP4032SS" (naphthalene type epoxy resin); "EXA-850CRP" (bisphenol A type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL "(bisphenol A type epoxy resin);" jER807 "," 1750 "(bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .;" jER152 "(phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YED-216D" (aliphatic epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase Chemtex. (Glysidyl ester type epoxy resin); "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "Seroxide 2021P" manufactured by Dycel Co., Ltd. Epoxy resin); "PB-3600" (epoxy resin having a butadiene structure) manufactured by Dycel Co., Ltd .; and the like. These may be used individually by 1 type, or may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and bixirenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF A type epoxy resin and a naphthylene ether type epoxy resin are more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalen type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200" (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" manufactured by DIC Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku Co., Ltd .; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YX8800" (anthracen type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (Fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. and the like can be mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more types.

(D) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is a mass ratio, preferably 1: 0.1 to 1. : 15, more preferably 1: 0.3 to 1:10, and particularly preferably 1: 0.6 to 1: 8. The quantitative ratio of the liquid epoxy resin to the solid epoxy resin in such a range usually provides appropriate adhesiveness when used in the form of a resin sheet. Further, when used in the form of a resin sheet, sufficient flexibility is usually obtained and handleability is improved. Further, usually, a cured product having sufficient breaking strength can be obtained.

The weight average molecular weight of the epoxy resin (D) is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The epoxy equivalent of the (D) epoxy resin is preferably within the same range as described as the range of the epoxy equivalent of the (A) glycidylamine type epoxy resin.

When the epoxy resin (D) is contained, the content of the epoxy resin (D) is preferably 0.5% by mass or more, more preferably 1% by mass when the non-volatile component in the sealing resin composition is 100% by mass. % Or more, more preferably 2% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less. (D) By keeping the amount of the epoxy resin within the above range, the mechanical strength and insulation reliability of the cured product of the sealing resin composition can be enhanced.

<(E) Curing agent>
The sealing resin composition may contain a curing agent as the component (E). The curing agent (E) usually has a function of reacting with an epoxy resin such as the component (A) and the component (D) to cure the sealing resin composition. (E) As the curing agent, one type may be used alone, or two or more types may be used in combination at any ratio.

As the curing agent (E), a compound capable of reacting with an epoxy resin to cure the resin composition can be used, for example, an amine-based curing agent, an acid anhydride-based curing agent, a phenol-based curing agent, and an activity. Examples thereof include an ester-based curing agent, a cyanate ester-based curing agent, a benzoxazine-based curing agent, and a carbodiimide-based curing agent. Above all, an amine-based curing agent is preferable from the viewpoint of being capable of low-temperature reaction and suppressing warpage of the cured product of the sealing resin composition.

Examples of the amine-based curing agent include curing agents having one or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-Diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, Examples thereof include bis (4- (3-aminophenoxy) phenyl) sulfone. Commercially available products may be used as the amine-based curing agent, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard AB", "Kayahard AB" manufactured by Nippon Kayaku Corporation. Examples include "Kayahard AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrohydride phthalic acid, methylhexahydrohydride phthalic acid, methylnadic acid anhydride, and hydride methylnadic acid. Anhydride, Trialkyltetrahydrophthalic anhydride, Dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-franyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, Trianhydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized, and the like.

Examples of the phenolic curing agent include a curing agent having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in one molecule. Of these, a compound having a hydroxyl group bonded to a benzene ring is preferable. Further, from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. In particular, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd .; manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH"; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN" manufactured by Nippon Steel & Sumitomo Metal Corporation -495 "," SN-495V "," SN-375 "," SN-395 ";" TD-2090 "," TD-2090-60M "," LA-7052 "," LA-7054 "manufactured by DIC. , "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" "; Examples thereof include "GDP-6115L", "GDP-6115H" and "ELPC75" manufactured by Gunei Chemical Co., Ltd.

Examples of the active ester-based curing agent include curing agents having one or more active ester groups in one molecule. Among them, as the active ester-based curing agent, two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. The compound to have is preferable. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compound, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Preferred specific examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl compound of phenol novolac. Examples include active ester compounds containing. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of the active ester-based curing agent include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", and "EXB9451", "EXB9460", "EXB9460S", and "EXB9451", "EXB9460S", and "HPC-8000H", as active ester compounds containing a dicyclopentadiene type diphenol structure. HPC-8000-65T "," HPC-8000H-65TM "," EXB-8000L "," EXB-8000L-65TM "," EXB-8150-65T "(manufactured by DIC); as an active ester compound containing a naphthalene structure. "EXB9416-70BK" (manufactured by DIC); "DC808" as an active ester compound containing an acetylated product of phenol novolac (manufactured by Mitsubishi Chemical Co., Ltd.); "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac. ); "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent that is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent that is a benzoylated product of phenol novolac. "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); and the like.

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylencyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidendiphenyl disyanate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Examples thereof include polyfunctional cyanate resins derived from phenol novolak, cresol novolak, and the like; prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" manufactured by Ronza Japan Co., Ltd. (both are phenol novolac type polyfunctional cyanate ester resins); "ULL-950S" (polyfunctional cyanate ester resin); BA230 ”,“ BA230S75 ”(prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer); and the like.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

The content of the curing agent (E) is preferably 0. When the non-volatile component in the sealing resin composition is 100% by mass from the viewpoint of improving the PCT test resistance, the compression mold moldability and the molding underfillability. 1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less. be.

When the number of epoxy groups of the component (A) is 1, the number of active groups of the (E) curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 0.3 or more. It is 2 or less, more preferably 1.8 or less, still more preferably 1.6 or less, and particularly preferably 1.4 or less. Here, the "number of epoxy groups of the epoxy resin" is a value obtained by adding all the values obtained by dividing the mass of the non-volatile component of the component (A) present in the sealing resin composition by the epoxy equivalent. The "(E) number of active groups of the curing agent" is a total of all the values obtained by dividing the mass of the non-volatile component of the (E) curing agent present in the sealing resin composition by the active group equivalent. .. When the number of active groups of the (E) curing agent is in the above range when the number of epoxy groups of the component (A) is 1, the desired effect of the present invention can be remarkably obtained, and more usually, a resin composition is used. The moisture resistance of the cured product of the layer is further improved.

<(F) Arbitrary additive>
The sealing resin composition may further contain an arbitrary additive as an arbitrary component in addition to the above-mentioned components. Examples of such additives include curing accelerators (excluding those corresponding to the component (B)); organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thermoplastic resins; thickening. Examples thereof include resin additives such as agents; antifoaming agents; leveling agents; adhesion-imparting agents; colorants; flame-retardant agents; and the like. One of these additives may be used alone, or two or more of these additives may be used in combination at any ratio.

The above-mentioned sealing resin composition may contain a solvent, if necessary, but it is preferably a solvent-free sealing resin composition that does not substantially contain a solvent. As described above, even if the solvent is not contained, the sealing resin composition can be fluidized when molded by the compression molding method, and excellent compression moldability can be realized. Therefore, this sealing resin composition can be used as a solvent-free resin composition. "Substantially free of solvent" means, for example, that the content of the solvent is 1% by mass or less with respect to the entire solvent-free resin composition.

[Manufacturing method of sealing resin composition]
The sealing resin composition can be produced, for example, by a method of stirring the compounding components using a stirring device such as a rotary mixer.

[Characteristics of encapsulating resin composition]
The above-mentioned sealing resin composition is excellent in filling property. Therefore, when the resin composition layer is formed on the circuit board or the semiconductor chip by the compression molding method, the sealing resin composition can be filled in every corner. Therefore, by curing the resin composition layer, it is possible to obtain a sealing layer having excellent sealing reliability and an insulating layer having excellent insulating reliability.

Further, the above-mentioned sealing resin composition has a characteristic of being excellent in compression mold moldability because it is excellent in filling property. Therefore, by using this sealing resin composition, it is possible to obtain a sealing layer and an insulating layer having excellent compression mold moldability. For example, by the method described in Examples, the above-mentioned sealing resin composition is compression-molded on a silicon wafer to form a resin composition layer. In this case, the resin composition layer usually reaches the entire silicon wafer.

Further, the above-mentioned sealing resin composition has a characteristic of being excellent in molding underfill property because it is excellent in filling property. Therefore, by using this sealing resin composition, it is possible to obtain a sealing layer and an insulating layer having excellent molding underfillability. For example, by the method described in Examples, the above-mentioned sealing resin composition is compression-molded on a silicon wafer on which a silicon chip is arranged to form a resin composition layer and heated. In this case, the cured product of the resin composition layer is usually filled in a state where there are no voids even in the lower portion of the silicon chip.

Further, the above-mentioned sealing resin composition can obtain a cured product having excellent high adhesion, that is, excellent PCT test resistance, even after being left in a high temperature and high humidity for a long time. Therefore, by using this sealing resin composition, a sealing layer and an insulating layer having excellent PCT test resistance can be obtained. For example, by the method described in Examples, a resin composition layer of the sealing resin composition is formed on a silicon wafer by using the above-mentioned sealing resin composition, and a PCT test is performed. In this case, usually, there is no peeling at the interface between the resin composition layer and the silicon wafer, and the resin composition layer is not chipped after cross-cutting.

The cured product using the above-mentioned sealing resin composition usually exhibits the characteristic that the generation of flow marks is suppressed. Therefore, by using this sealing resin composition, it is possible to obtain a sealing layer and an insulating layer in which the generation of flow marks is suppressed. For example, by the method described in Examples, the above-mentioned sealing resin composition is compression-molded on a silicon wafer to form a resin composition layer and heated to obtain a cured product layer. In this case, the generation of flow marks on the surface of the cured product is usually suppressed.

Further, the above-mentioned sealing resin composition usually exhibits a characteristic of low viscosity. Therefore, by using this sealing resin composition, the handleability when performing compression molding using the compression molding device becomes excellent. For example, using a RE80 type viscometer (measurement target sealing resin composition 0.2 to 0.3 ml, measuring chamber temperature 25.0 ° C.), the rotor rotation speed is set to 1 rpm, and the viscosity after 120 seconds. To measure. In this case, the viscosity of the sealing resin composition can be usually 600 Pa · s or less, preferably 500 Pa · s or less, and more preferably 150 Pa · s or less. There is no particular limitation on the upper limit, and it can usually be 0.1 Pa · s or more.

The sealing resin composition may be in a liquid state or in a solid state, but is preferably in a liquid state at the time of molding. For example, the encapsulating resin composition that is liquid at room temperature (for example, 20 ° C.) may be molded by a compression molding method at room temperature without any special temperature adjustment, and may be compression-molded by heating to an appropriate temperature. Molding by the method may be performed. Further, the sealing resin composition which is liquid at room temperature may be filled in the cartridge, the sealing resin composition may be discharged from the cartridge, and then molding by a compression molding method may be performed.

Further, since the sealing resin composition which is solid at room temperature can be liquefied by adjusting the temperature to a higher temperature (for example, 130 ° C.), the compression molding method is performed by appropriate temperature adjustment such as heating. Can be molded by. The sealing resin composition can usually be liquid at an appropriate temperature without containing a solvent, and can be used as a liquid sealing material, for example. Here, the liquid means that the viscosity measured by the measuring method described in [Measurement of Viscosity] described later is less than 1500 Pa · s.

Since the encapsulating resin composition has the above-mentioned characteristics, it can be suitably used as a resin composition for encapsulating electronic devices such as organic EL devices and semiconductors, and particularly for encapsulating semiconductors. Can be suitably used as a resin composition (resin composition for encapsulating a semiconductor), preferably a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). Further, the sealing resin composition can be used as a resin composition for an insulating layer other than the sealing use. For example, the sealing resin composition includes a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package) and a circuit board (printed wiring board). ) Can be suitably used as a resin composition (resin composition for an insulating layer of a circuit board) for forming an insulating layer.

Examples of the semiconductor chip package include FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), and the like. Fan-in type PLP can be mentioned.

Further, the sealing resin composition may be used as an underfill material, or may be used, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

Further, the sealing resin composition is used in a wide range of applications such as a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, a die bonding material, a hole filling resin, a component filling resin, and the like. Can be used for.

[Resin sheet]
The resin sheet of the present invention has a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the sealing resin composition of the present invention, and is usually formed of the sealing resin composition.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, still more preferably 500 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, or 200 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more, 5 μm or more, 10 μm or more, and the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). Polyethylene such as (.); Polyethylene (hereinafter abbreviated as "PC"); Acrylic polymer such as polymethylmethacrylate (hereinafter abbreviated as "PMMA"); Cyclic polyolefin; Triacetyl cellulose (hereinafter abbreviated as "PC"). "TAC" may be abbreviated.); Polyether sulfide (hereinafter, may be abbreviated as "PES"); Polyether ketone; Polyethylene; and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Of these, copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be treated with a matte treatment, a corona treatment, an antistatic treatment, or the like.

Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based mold release agents. Examples of the support with a release layer include "Lumirror T60" manufactured by Toray Industries, Inc .; "Purex" manufactured by Teijin Ltd.; and "Unipee" manufactured by Unitika Ltd.

The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

The resin sheet can be produced, for example, by applying a sealing resin composition onto a support using a coating device such as a die coater. Further, if necessary, the sealing resin composition may be dissolved in an organic solvent to prepare a resin varnish, and the resin varnish may be applied to produce a resin sheet. By using a solvent, the viscosity can be adjusted and the coatability can be improved. When a resin varnish is used, the resin varnish is usually dried after application to form a resin composition layer.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitol such as cellosolve and butyl carbitol. Solvents; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. The organic solvent may be used alone or in combination of two or more at any ratio.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A layer can be formed.

The resin sheet may include any layer other than the support and the resin composition layer, if necessary. For example, in the resin sheet, a protective film similar to the support may be provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust and the like from adhering to the surface of the resin composition layer and scratches. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, the resin sheet can be rolled up and stored.

[Circuit board]
The circuit board used in the present invention can be manufactured, for example, by a manufacturing method including the following steps (1) and (2). The cured product of the above-mentioned sealing resin composition is used as a sealing layer for a semiconductor chip or the like on a circuit board as described later, and the insulating layer contained in the circuit board is cured of the sealing resin composition. It may be formed by an object. However, the insulating layer may be formed of a material other than the cured product of the sealing resin composition described above.
(1) A step of forming a resin composition layer on a substrate.
(2) A step of thermally curing the resin composition layer to form an insulating layer.

In step (1), a base material is prepared. Examples of the base material include a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Further, the base material may have a metal layer such as a copper foil on the surface as a part of the base material. For example, a substrate having a peelable first metal layer and a second metal layer on both surfaces may be used. When such a base material is used, a conductor layer as a wiring layer that can function as a circuit wiring is usually formed on a surface of the second metal layer opposite to the first metal layer. Examples of the base material having such a metal layer include ultra-thin copper foil "Micro Tin" with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd.

Further, a conductor layer may be formed on one or both surfaces of the base material. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be appropriately referred to as a “base material with a wiring layer”. As the conductor material contained in the conductor layer, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Materials containing the above metals can be mentioned. As the conductor material, a single metal may be used or an alloy may be used. Examples of the alloy include alloys of two or more kinds of metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal; and nickel-chromium alloy as an alloy from the viewpoint of versatility, cost, and ease of patterning for forming a conductor layer. , Copper / nickel alloys, copper / titanium alloys; are preferred. Among them, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and a nickel-chromium alloy; are more preferable, and a single metal of copper is particularly preferable.

The conductor layer may be patterned, for example, to function as a wiring layer. At this time, the line (circuit width) / space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and further. It is preferably 5/5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not have to be the same throughout the conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

The conductor layer is, for example, a step of laminating a dry film (photosensitive resist film) on a substrate, exposing and developing the dry film under predetermined conditions using a photoresist to form a pattern, and pattern drying. It can be formed by a method including a step of obtaining a film, a step of forming a conductor layer by a plating method such as an electrolytic plating method using a developed pattern dry film as a plating mask, and a step of peeling off the pattern dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolak resin or an acrylic resin can be used. The laminating conditions of the base material and the dry film may be the same as the laminating conditions of the base material and the resin sheet described later. The peeling of the dry film can be carried out using, for example, an alkaline stripping solution such as a sodium hydroxide solution.

After preparing the base material, a resin composition layer is formed on the base material. When the conductor layer is formed on the surface of the base material, it is preferable to form the resin composition layer so that the conductor layer is embedded in the resin composition layer.

The formation of the resin composition layer is performed, for example, by laminating a resin sheet and a base material. This lamination can be performed, for example, by heat-pressing the resin sheet to the base material from the support side to attach the resin composition layer to the base material. Examples of the member for heat-crimping the resin sheet to the base material (hereinafter, may be referred to as “heat-crimping member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll, etc.). Be done. It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the base material.

Lamination of the base material and the resin sheet may be carried out by, for example, a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C. The heat crimping pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 13 hPa or less.

After laminating, the laminated resin sheet may be smoothed by pressing under normal pressure (under atmospheric pressure), for example, from the support side. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The laminating and smoothing treatment may be continuously performed using a vacuum laminator.

The resin composition layer may be formed from the resin sheet of the present invention or the sealing resin composition. When the resin composition layer is formed from the sealing resin composition, the resin composition layer can be formed, for example, by a compression molding method. Further, the resin composition layer may be formed by filling the cartridge with the sealing resin composition and discharging the sealing resin composition from the cartridge. As the molding conditions, the same conditions as the method for forming the resin composition layer in the step of forming the sealing layer of the semiconductor chip package described later may be adopted.

After forming the resin composition layer on the base material, the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer differ depending on the type of the resin composition, but the curing temperature is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably 170 ° C. to 200 ° C.). The curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). May be preheated for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, a circuit board having an insulating layer can be manufactured. Further, the method for manufacturing a circuit board may further include an arbitrary step.
For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing the circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled off before the thermosetting of the resin composition layer, or may be peeled off after the thermosetting of the resin composition layer.

The method for manufacturing a circuit board may include, for example, a step of polishing the surface of the insulating layer after forming the insulating layer. The polishing method is not particularly limited. For example, the surface of the insulating layer can be polished using a surface grinding machine.

The method for manufacturing a circuit board may include, for example, a step (3) of interlayer connection of conductor layers, a step of drilling holes in a so-called insulating layer. As a result, holes such as via holes and through holes can be formed in the insulating layer. Examples of the method for forming the via hole include laser irradiation, etching, and mechanical drilling. The size and shape of the via hole may be appropriately determined according to the design of the circuit board. In the step (3), the interlayer connection may be performed by polishing or grinding the insulating layer.

After forming the via hole, it is preferable to perform a step of removing the smear in the via hole. This process is sometimes referred to as the desmear process. For example, when the conductor layer is formed on the insulating layer by the plating step, the via hole may be subjected to a wet desmear treatment. Further, when the conductor layer is formed on the insulating layer by a sputtering step, a dry desmear step such as a plasma treatment step may be performed. Further, the insulating layer may be roughened by the desmear step.

Further, the insulating layer may be roughened before the conductor layer is formed on the insulating layer. According to this roughening treatment, the surface of the insulating layer including the inside of the via hole is usually roughened. As the roughening treatment, either a dry type or a wet type roughening treatment may be performed. Examples of the dry roughening treatment include plasma treatment and the like. Further, as an example of the wet roughening treatment, there is a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

After forming the via hole, a conductor layer is formed on the insulating layer. By forming the conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base material are made conductive, and the interlayer connection is performed. Examples of the method for forming the conductor layer include a plating method, a sputtering method, a vapor deposition method, and the like, and the plating method is particularly preferable. In a preferred embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Further, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by the subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Further, the conductor layer may have a single-layer structure, or may have a multi-layer structure including two or more layers of different types of materials.

Here, an example of an embodiment in which the conductor layer is formed on the insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. After forming an electrolytic plating layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by a treatment such as etching to form a conductor layer having a desired wiring pattern. When forming the conductor layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

The method for manufacturing a circuit board may include a step (4) of removing a base material. By removing the base material, a circuit board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. This step (4) can be performed, for example, when a substrate having a peelable metal layer is used.

[Semiconductor chip package]
The semiconductor chip package according to the first embodiment of the present invention is a cured product of the sealing resin composition of the present invention for encapsulating the above-mentioned circuit board, the semiconductor chip mounted on the circuit board, and the semiconductor chip. And include. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

The semiconductor chip can be sealed by the same method as in step (C) in the second embodiment described later.

As the bonding condition between the circuit board and the semiconductor chip, any condition can be adopted in which the terminal electrode of the semiconductor chip and the circuit wiring of the circuit board can be connected by a conductor. For example, the conditions used in flip-chip mounting of semiconductor chips can be adopted. Further, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

An example of the joining method is a method of crimping a semiconductor chip to a circuit board. As the crimping conditions, the crimping temperature is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 130 ° C. to 200 ° C., more preferably in the range of 140 ° C. to 180 ° C.), and the crimping time is usually in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).

Further, as another example of the joining method, there is a method of reflowing a semiconductor chip to a circuit board and joining. The reflow condition may be in the range of 120 ° C to 300 ° C.

After joining the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the above-mentioned sealing resin composition may be used, or the above-mentioned resin sheet may be used.

The semiconductor chip package according to the second embodiment of the present invention includes a semiconductor chip and a cured product of the sealing resin composition for encapsulating the semiconductor chip. Examples of the semiconductor chip package according to the second embodiment include a fan-out type WLP.

The manufacturing method of such a semiconductor chip package is
(A) Step of laminating a temporary fixing film on a base material,
(B) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(C) A step of forming a sealing layer on a semiconductor chip,
(D) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.
(F) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer, and
(G) A step of forming a solder resist layer on the rewiring layer,
including. Further, the method for manufacturing the above-mentioned semiconductor chip package is as follows.
(H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and individualizing them may be included.

(Step (A))
The step (A) is a step of laminating a temporary fixing film on the base material. The laminating conditions of the base material and the temporary fixing film may be the same as the laminating conditions of the base material and the resin sheet in the method for manufacturing a circuit board.

As the base material, for example, silicon wafer; glass wafer; glass substrate; copper, titanium, stainless steel, metal substrate such as cold rolled steel plate (SPCC); FR-4 substrate or the like, the glass fiber is impregnated with epoxy resin or the like. Examples thereof include a heat-cured substrate; a substrate made of a bismaleimide triazine resin such as a BT resin; and the like.

As the temporary fixing film, any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used. Examples of commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

(Step (B))
The step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporary fixing of the semiconductor chip can be performed by using a device such as a flip chip bonder or a die bonder, for example. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor package, and the like. For example, semiconductor chips may be temporarily fixed by arranging the semiconductor chips in a matrix having a plurality of rows and a plurality of columns.

(Process (C))
The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed by the cured product of the above-mentioned sealing resin composition. The sealing layer is usually formed by a method including a step of forming a sealing resin composition layer on a semiconductor chip and a step of thermally curing the resin composition layer to form a sealing layer.

Taking advantage of the excellent compression moldability of the sealing resin composition, it is preferable that the resin composition layer is formed by a compression molding method. In the compression molding method, a semiconductor chip and a resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the sealing resin composition in the mold to form a resin composition layer covering the semiconductor chip. Form.

The specific operation of the compression molding method can be, for example, as follows. As the mold for compression molding, an upper mold and a lower mold are prepared. Further, the sealing resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the sealing resin composition is attached to the lower mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are molded, and heat and pressure are applied to the sealing resin composition to perform compression molding.

Further, the specific operation of the compression molding method may be as follows, for example. As the mold for compression molding, an upper mold and a lower mold are prepared. Place the sealing resin composition on the lower mold. Further, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are molded so that the sealing resin composition placed on the lower mold comes into contact with the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

The molding conditions differ depending on the composition of the sealing resin composition, and appropriate conditions can be adopted so that good sealing is achieved. For example, the temperature of the mold at the time of molding is preferably a temperature at which the sealing resin composition can exhibit excellent compression moldability, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. It is preferably 200 ° C. or lower, more preferably 170 ° C. or lower, and particularly preferably 150 ° C. or lower. The pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, preferably 50 MPa or less, more preferably 30 MPa or less, and particularly preferably 20 MPa or less. The cure time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Usually, the mold is removed after the formation of the resin composition layer. The mold may be removed before the thermosetting of the resin composition layer or after the thermosetting.

The compression molding method may be performed by discharging the sealing resin composition filled in the cartridge to the lower mold. The molding conditions after the formation of the resin composition layer are the same as the conditions in the compression molding.

The resin composition layer may be formed by laminating a resin sheet and a semiconductor chip. For example, a resin composition layer can be formed on a semiconductor chip by heat-pressing the resin composition layer of the resin sheet and the semiconductor chip. The laminating of the resin sheet and the semiconductor chip can usually be performed by using the semiconductor chip instead of the base material in the same manner as the laminating of the resin sheet and the base material in the method for manufacturing a circuit board.

After forming the resin composition layer on the semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. As a result, the semiconductor chip is sealed with the cured product of the sealing resin composition. As the thermosetting condition of the resin composition layer, the same conditions as the thermosetting condition of the resin composition layer in the method for manufacturing a circuit board may be adopted. Further, before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. As the treatment conditions for this preheat treatment, the same conditions as those for the preheat treatment in the method for manufacturing a circuit board may be adopted.

(Step (D))
The step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. As the peeling method, it is desirable to adopt an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming or expanding the temporary fixing film to peel it off. Further, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through a base material to reduce the adhesive force of the temporary fixing film and peeling the film can be mentioned.

In the method of heating, foaming or expanding the temporary fixing film to peel it off, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method of irradiating with ultraviolet rays to reduce the adhesive strength of the temporary fixing film and peeling it off, the irradiation amount of the ultraviolet rays is usually 10 mJ / cm ² to 1000 mJ / cm ² .

(Step (E))
The step (E) is a step of forming a rewiring forming layer as an insulating layer on the surface from which the base material of the semiconductor chip and the temporary fixing film have been peeled off.

As the material of the rewiring cambium, any material having an insulating property can be used. Of these, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, you may use the sealing resin composition of this invention as this thermosetting resin.

After forming the rewiring cambium, via holes may be formed in the rewiring cambium in order to interconnect the semiconductor chip and the rewiring layer.

In the method of forming a via hole when the material of the rewiring cambium is a photosensitive resin, the surface of the rewiring cambium is usually irradiated with active energy rays through a mask pattern to illuminate the rewiring cambium of the irradiated portion. Cure. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. Examples of the exposure method include a contact exposure method in which the mask pattern is brought into close contact with the rewiring cambium and exposed, and a non-contact exposure method in which the mask pattern is exposed using parallel light rays without being brought into close contact with the rewiring cambium. Can be mentioned.

After the rewiring cambium is photo-cured, the rewiring cambium is developed and the unexposed portion is removed to form a via hole. The development may be either wet development or dry development. Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

Examples of the method for forming the via hole when the material of the rewiring forming layer is a thermosetting resin include laser irradiation, etching, and mechanical drilling. Above all, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide gas laser, a UV-YAG laser, or an excimer laser.

The shape of the via hole is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, further preferably 20 μm or less, preferably 3 μm or more, preferably 10 μm or more, and more preferably 15 μm or more. Here, the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring cambium.

(Step (F))
The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring forming layer may be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing a circuit board. Further, the step (E) and the step (F) may be repeated, and the rewiring layer and the rewiring forming layer may be alternately stacked (build-up).

(Process (G))
The step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any material having an insulating property can be used. Of these, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, you may use the sealing resin composition of this invention as a thermosetting resin.

Further, in the step (G), bumping may be performed to form bumps, if necessary. The bumping process can be performed by a method such as solder balls or solder plating. Further, the formation of the via hole in the bumping process can be performed in the same manner as in the step (E).

The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and individualizing them. The method of dicing a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

The semiconductor chip package according to the third embodiment of the present invention is, for example, in the semiconductor chip package of the second embodiment, a semiconductor chip package in which a rewiring forming layer or a solder resist layer is formed of a cured product of the resin composition of the present invention. Is.

[Semiconductor device]
Examples of the semiconductor device on which the above-mentioned semiconductor chip package is mounted include electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (for example, TVs). , Motorcycles, automobiles, trains, ships, aircraft, etc.).

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

<Synthesis Example 1: Synthesis of Compound A>
2-Methylimidazole (82.1 g, 1 mol) and 2-naphthol (144.0 g, 1 mol) are added to isopropanol (400.0 g), and formalin (37% aqueous solution, CH _2O 1 mol) is further added. It was added over 30 minutes at room temperature. Then, the reaction mixture was stirred at room temperature for 40 minutes and then at 85 ° C. for 4 hours. The mixture was then cooled to room temperature and filtered. The filtrate was ground and dried under reduced pressure at 60 ° C. to obtain a product (white powder) represented by the formula (2) in a yield of 78%.

From the analysis result by the differential operating calorimeter (DSC), the melting point of compound A was 210 ° C. In addition, ¹ H-NMR spectrum and ¹³ C-NMR spectrum were analyzed. The measured NMR spectrum data was as follows.
^{1 1} H-NMR (400 MHz, DMSO-d ₆ ): 2.44 (s, 3H), 5.40 (s, 2H), 6.57 (d, 2H, J = 6.0 Hz), 7.25 ( d, 1H, J = 7.2Hz), 7.31 (dd, 1H, J = 5.6Hz, 6.4Hz), 7.47 (dd, 1H, J = 5.6Hz, 6.8Hz), 7 .84 (m, 3H), 10.14 (s, 1H)
¹³ C-NMR (100 MHz, DMSO-d ₆ ): 13.6, 39.6, 113.5, 118.6, 119.2, 122.7, 123.2, 126.4, 127.5, 128 .7, 129.1, 130.7, 133.6, 144.4, 154.5

<Inorganic filler used>
Silica A: Spherical silica treated with an average particle size of 1.5 μm, a maximum cut diameter of 5 μm, a specific surface area of 3.4 m ² / g, and KBM573 (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.).
Silica B: Spherical silica treated with an average particle size of 1.3 μm, a maximum cut diameter of 5 μm, a specific surface area of 3.0 m ² / g, and KBM403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.).

[Preparation of resin composition for encapsulation]
<Example 1>
5 parts of glycidylamine type epoxy resin ("EP3980S" manufactured by ADEKA, epoxy equivalent 115 g / eq.), 7 parts of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 95 g / eq.), Bisphenol A type Epoxy resin (“EXA-850CRP” manufactured by DIC, epoxy equivalent 170 to 175 g / eq.), 72 parts of silica A, 1.5 parts of compound A are uniformly dispersed using a mixer to seal the resin. The composition was obtained.

In addition, "EP3980S" and "630" are represented by the following structural formulas.

<Example 2>
In Example 1, the amount of bisphenol A type epoxy resin (“EXA-850CRP” manufactured by DIC Corporation, epoxy equivalent 170 to 175 g / eq.) Was changed from 3 parts to 2 parts, and further, dimer acid glycidyl ester (manufactured by Mitsubishi Chemical Corporation). "JER871", epoxy equivalent 412 g / eq.) 1 part was added. A resin composition for sealing was obtained in the same manner as in Example 1 except for the above items.

<Example 3>
In Example 1, 72 parts of silica A was changed to 72 parts of silica B. A resin composition for sealing was obtained in the same manner as in Example 1 except for the above items.

<Example 4>
In Example 1, 0.5 part of diphenylaminosulfone was further added. A resin composition for sealing was obtained in the same manner as in Example 1 except for the above items.

<Comparative Example 1>
In Example 1,
1) Change 1.5 parts of compound A to 0.4 parts of curing accelerator ("2E4MZ" manufactured by Shikoku Chemicals Corporation).
2) Change the amount of bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC, epoxy equivalent 170-175 g / eq.) From 3 parts to 4 parts.
3) 72 parts of silica A was changed to 72 parts of silica B. A resin composition for sealing was obtained in the same manner as in Example 1 except for the above items.

<Comparative Example 2>
In Example 1,
1) No glycidylamine type epoxy resin ("EP3980S" manufactured by ADEKA, epoxy equivalent 115 g / eq.) Was added.
2) Change the amount of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent 95 g / eq.) From 7 parts to 2 parts.
3) The amount of bisphenol A type epoxy resin (“EXA-850CRP” manufactured by DIC Corporation, epoxy equivalent 170 to 175 g / eq.) Was changed from 3 parts to 13 parts. A resin composition for sealing was obtained in the same manner as in Example 1 except for the above items.

<Comparative Example 3>
In Example 1,
1) Change the amount of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent 95 g / eq.) From 7 parts to 15 parts.
2) No bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC, epoxy equivalent 170 to 175 g / eq.) Was added.
3) The amount of silica A was changed from 72 parts to 88 parts. A resin composition for sealing was obtained in the same manner as in Example 1 except for the above items.

[Evaluation of flow mark]
The sealing resin compositions prepared in Examples and Comparative Examples were compression-molded on a 12-inch silicon wafer using a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). A resin composition layer having a thickness of 300 μm was formed. Then, after heating at 150 ° C. for 60 minutes, the flow mark was visually confirmed on the surface of the resin composition layer. Those having a flow mark on the entire wafer were marked with "x", those with a flow mark only at the end of the wafer were marked with "Δ", and those without a flow mark were marked with "○".

[PCT test]
The sealing resin compositions prepared in Examples and Comparative Examples were compression-molded on a 12-inch silicon wafer using a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). A resin composition layer having a thickness of 300 μm was formed. Then, after heating at 150 ° C. for 60 minutes, a PCT test (Pressure Cooker Test) in which the product is left for 100 hours in an environment of 121.5 ° C. and 100% RH using an advanced accelerated life test device (PM422 manufactured by ETAC). Was carried out. After that, the temperature was returned to room temperature, and a cross cut (a grid-like notch having a width of 1 mm) was made on the surface of the resin composition layer, and it was confirmed whether the resin composition layer had a chip.

The case where the resin composition layer and the silicon wafer interface are not peeled off and the resin composition layer is not chipped after cross-cutting is marked with "○", and the resin composition layer and the silicon wafer interface are not peeled off and the resin is not peeled off after cross-cutting. The case where the composition layer is chipped is designated as “Δ”, and the case where the resin composition layer and the silicon wafer interface are peeled off and the resin composition layer is chipped after cross-cutting is designated as “x”.

[Evaluation of compression mold formability]
The sealing resin compositions prepared in Examples and Comparative Examples were compression-molded on a 12-inch silicon wafer using a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). A resin composition layer having a thickness of 300 μm was formed.

The resin composition layer is perfect on the entire contact area between the upper mold of the compression mold device and the sealing resin composition, and the one with good filling property is "○", and the upper mold and the sealing resin composition The one in which the resin composition layer did not reach the entire contact portion with the resin was defined as "unfilled".

[Measurement of viscosity]
With a RE80 type viscometer (manufactured by Toki Sangyo Co., Ltd.), 0.2 to 0.3 ml of the sealing resin composition to be measured was weighed with a syringe. At the time of measurement, the temperature of the measuring chamber of the viscometer was controlled to 25.0 ° C. in an external circulation type constant temperature bath. The rotation speed of the rotor was set to 1 rpm, and the viscosity after 120 seconds was measured (unit: Pa · s).

[Evaluation of molding underfillability]
50 1 cm square silicon chips are arranged on a 12-inch silicon wafer via bumps (height 50 μm, pitch 50 μm, size 40 μm), and the encapsulation resin composition produced in Examples and Comparative Examples is prepared from above. , Molded with a compression molding device (mold temperature: 130 ° C., pressure: 8 MPa, cure time: 10 minutes). After the sample obtained by molding is heat-treated in an oven at 150 ° C. for 60 minutes, it is determined whether or not the portion under the silicon chip is filled with the cured product of the sealing resin composition. Confirmed by (SAT).

Those filled with the cured product of the resin composition layer were evaluated as "no voids", and those filled with the cured product of the resin composition layer having an area of 1 square millimeter or more were evaluated as "with voids".

＊表中、（Ｃ）成分の含有量は、封止用樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｃ）成分の含有量を表す。

* In the table, the content of the component (C) represents the content of the component (C) when the non-volatile component in the sealing resin composition is 100% by mass.

In Examples 1 to 4, it has been confirmed that even when the component (D) and the component (E) are not contained, the same result as in the above-mentioned Examples is obtained, although the degree is different.

Claims (12)

(A) Glycidylamine type epoxy resin,
A sealing resin composition containing (B) a compound represented by the following general formula (1) and (C) an inorganic filler.
When the non-volatile component in the sealing resin composition is 100% by mass, the content of the component (A) is 3% by mass or more and 15% by mass or less, and the content of the component (B) is 0. A resin composition for sealing , which is 5% by mass or more and 5% by mass or less .

(In formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R, respectively. ¹⁰ independently represents a hydrogen atom, a methyl group, or a hydroxyl group.) The sealing resin composition according to claim 1, wherein the component (A) is a bifunctional or trifunctional glycidylamine type epoxy resin. The sealing resin composition according to claim 1 or 2, wherein at least one of R ⁴ to R ¹⁰ in the general formula (1) represents a hydroxyl group. The sealing resin composition according to claim 3, wherein in the general formula (1), R ⁴ to R ⁹ independently represent a hydrogen atom, a methyl group, or a hydroxyl group, and R ¹⁰ is a hydroxyl group. .. The sealing resin composition according to any one of claims 1 to 4, wherein at least one of R ¹ to R ³ in the general formula (1) represents a methyl group. The sealing resin composition according to any one of claims 1 to 5, wherein the component (B) is represented by the following formula (2).

The sealing according to any one of claims 1 to 6, wherein the content of the component (A) is 5% by mass or more when the non-volatile component in the sealing resin composition is 100% by mass. Resin composition. The content of the component (C) is 80% by mass or more and 95% by mass or less when the non-volatile component in the sealing resin composition is 100% by mass, according to any one of claims 1 to 7. Resin composition for encapsulation. The sealing resin composition according to any one of claims 1 to 8, wherein the average particle size of the component (C) is 0.1 μm or more and 10 μm or less. The sealing resin composition according to any one of claims 1 to 9, which is a liquid sealing resin composition. A semiconductor chip including a circuit board, a semiconductor chip mounted on the circuit board, and a cured product of the sealing resin composition according to any one of claims 1 to 10 for sealing the semiconductor chip. package. A semiconductor chip package comprising a semiconductor chip and a cured product of the encapsulating resin composition according to any one of claims 1 to 10.