JP7225546B2 - Sealing resin composition - Google Patents

Description

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

In recent years, there has been an increase in demand for small, highly functional electronic devices such as smart phones and tablet-type devices, and along with this, 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 Patent Documents 1 and 2, for example).

JP 2014-55233 A JP 2014-177530 A

In recent years, there has been a demand for a smaller semiconductor chip package, and accordingly, it is required to reduce the thickness of the insulating layer used in the semiconductor chip package and the silicon chip itself. Therefore, it is desired to develop an insulating layer that can suppress warping even if the thickness is thin. Furthermore, the insulating layer is required to have high adhesion even after repeated heating and cooling. is required. However, conventional resin compositions still have room for improvement in the evaluation of warpage and adhesion.

The resin composition used for forming the insulating layer may also be used as a sealing material for semiconductor chip packages. For example, it is conceivable to use a cured product obtained by curing a resin composition as a sealing layer for sealing a semiconductor chip in a semiconductor chip package. The above-described problems also arise when the resin composition is used as a sealing material for semiconductor chip packages.

The present invention was invented in view of the above problems, and is a sealing resin that can suppress warping and can obtain a cured product having high adhesion (thermal cycle test resistance) even after repeated heating and cooling. An object of the present invention is to provide a composition; and a semiconductor chip package containing a cured product of the sealing resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found that the resin composition contains predetermined amounts of (A) a glycidylamine type epoxy resin and (B) a glycidyl ester type epoxy resin, thereby reducing warpage. The inventors have found that it is possible to obtain a sealing resin composition that can be suppressed and that can obtain a cured product having high adhesion even after repeated heating and cooling, and have completed the present invention. That is, the present invention includes the following.

[1] (A) glycidylamine type epoxy resin,
(B) a glycidyl ester type epoxy resin,
(C) a curing agent, and (D) an inorganic filler, a sealing resin composition containing
An encapsulating resin composition in which the content of component (A) is 3% by mass or more and 15% by mass or less when the non-volatile component in the encapsulating resin composition is 100% by mass.
[2] The encapsulating resin composition according to [1], wherein component (A) is a bifunctional or trifunctional glycidylamine type epoxy resin.
[3] The resin composition for sealing according to [1] or [2], wherein the component (B) contains a dimer acid-modified glycidyl ester type epoxy resin.
[4] A1 is the content of component (A) when the non-volatile component in the encapsulating resin composition is 100% by mass, and the non-volatile component in the encapsulating resin composition is 100% by mass. The encapsulating resin composition according to any one of [1] to [3], wherein a1/b1 is 0.6 or more and 30 or less, where b1 is the content of component (B).
[5] The content of component (B) is 0.5% by mass or more and 5% by mass or less when the non-volatile component in the encapsulating resin composition is 100% by mass [1] to [4] 3. The encapsulating resin composition according to any one of .
[6] The content of component (C) is 0.1% by mass or more and 3% by mass or less when the non-volatile component in the encapsulating resin composition is 100% by mass [1] to [5] 3. The encapsulating resin composition according to any one of .
[7] The encapsulating resin composition according to any one of [1] to [6], wherein component (C) contains an amine-based curing agent.
[8] Any of [1] to [7], wherein the content of component (D) 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 encapsulating resin composition according to (1).
[9] The encapsulating resin composition according to any one of [1] to [8], wherein component (D) has an average particle size of 0.1 μm or more and 10 μm or less.
[10] The resin composition for sealing according to any one of [1] to [9], wherein component (D) is silica or alumina.
[11] The encapsulating resin composition according to any one of [1] to [10], which is a liquid encapsulating resin composition.
[12] The sealing resin composition according to any one of [1] to [11], wherein the sealing resin composition has a minimum melt viscosity from 60°C to 200°C of 50 poise or more and 400 poise or less.
[13] 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 [12] for sealing the semiconductor chip. , semiconductor chip package.
[14] A semiconductor chip package comprising a semiconductor chip and a cured product of the encapsulating resin composition according to any one of [1] to [12] for encapsulating the semiconductor chip.

According to the present invention, a sealing resin composition capable of suppressing warping and obtaining a cured product having high adhesion even after repeated heating and cooling, and a cured product of the sealing resin composition are provided. a semiconductor chip package;

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents. In the present invention, the content of each component in the encapsulating resin composition is a value when the non-volatile component in the encapsulating resin composition is 100% by mass, unless otherwise specified.

[Resin composition for encapsulation]
The encapsulating resin composition of the present invention contains (A) a glycidylamine type epoxy resin, (B) a glycidyl ester type epoxy resin, (C) a curing agent, and (D) an inorganic filler. It is a resin composition, and when the non-volatile component in the sealing resin composition is 100% by mass, the content of component (A) is 3% by mass or more and 15% by mass or less. (A) the glycidylamine type epoxy resin, (B) the glycidyl ester type epoxy resin, (C) the curing agent, and (D) the inorganic filler in combination, and the content of (A) the glycidylamine type epoxy resin Within a predetermined range, the encapsulating resin composition can suppress warping, and obtain the desired effect of the present invention that a cured product having high adhesion even after repeated heating and cooling can be obtained. be able to. The cured product of this resin composition for sealing 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 is combined with (A) a glycidylamine type epoxy resin, (B) a glycidyl ester type epoxy resin, (C) a curing agent, and (D) an inorganic filler, and further optionally may contain ingredients. Optional components include, for example, (E) an epoxy resin and (F) a curing accelerator. Each component contained in the encapsulating resin composition will be described below.

<(A) Glycidylamine type epoxy resin>
The encapsulating resin composition contains a glycidylamine-type epoxy resin as component (A). , the content is 3% by mass or more and 15% by mass or less. Since heat resistance can be improved by including a predetermined amount of (A) glycidylamine type epoxy resin in the resin composition for sealing, thermal cycle test resistance can be improved. In addition, by including a predetermined amount of (A) glycidylamine type epoxy resin, it is possible to reduce the coefficient of thermal expansion (CTE, sometimes referred to as coefficient of thermal expansion), and as a result, suppress warpage. It becomes possible to Furthermore, it is also possible to reduce the viscosity of the encapsulating resin composition by adding a predetermined amount of (A) the glycidylamine type epoxy resin to the encapsulating resin composition.

(A) As the glycidylamine type epoxy resin, an epoxy resin in which a glycidyl group is directly bonded to a nitrogen atom can be used. Among them, from the viewpoint of further improving heat resistance and lowering the coefficient of linear thermal expansion, it is preferably a bifunctional or trifunctional glycidylamine type epoxy resin, more preferably a trifunctional glycidylamine type epoxy resin. preferable. (A) As the glycidylamine type epoxy resin, a bifunctional glycidylamine type epoxy resin and a trifunctional glycidylamine type epoxy resin may be used in combination. For example, a trifunctional glycidylamine-type epoxy resin represents a glycidylamine-type epoxy resin having three epoxy groups in the molecule.

(A) The 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。） (A) The glycidylamine type epoxy resin is preferably represented by the following formula (A).

(In formula (A), R ¹¹ each independently represents a glycidyl ether group or an alkyl group having 1 to 6 carbon atoms; R ¹² is a hydrogen atom or a monovalent to trivalent represents a hydrocarbon group, n independently represents an integer of 0 to 4, and m represents an integer of 1 to 3.)

Each 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 further preferably a methyl group. The alkyl group having 1 to 6 carbon atoms is preferably bonded at the ortho position with respect to the bonding site between the nitrogen atom and the aromatic ring. Among them, from the viewpoint of obtaining the desired effects of the present invention, R ¹¹ is preferably a glycidyl ether group, and the glycidyl ether group is preferably bonded to the para-position with respect to the bonding site of the nitrogen atom and the aromatic ring. .

R ¹² represents a hydrogen atom or a monovalent to trivalent hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group having 1 to 10 carbon atoms includes an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, a trivalent group derived from an alkyl group having 1 to 10 carbon atoms, Examples include an aryl group having 6 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, and the like. 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. Arylene groups having 6 to 10 carbon atoms include phenylene groups and naphthylene groups. Among them, when m is 1, from the viewpoint of obtaining the desired effects of the present invention, R ¹² is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group. When m is 2, R ¹² is preferably an alkylene group having 1 to 10 carbon atoms, more preferably a methylene group, from the viewpoint of obtaining the desired effects of the present invention.

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

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

(A) Glycidylamine-type epoxy resins may be used singly or in combination of two or more at any ratio.

(A) The glycidylamine-type epoxy resin is 3% by mass or more, preferably 4% by mass or more, more preferably 5% by mass or more, when the non-volatile component in the sealing resin composition is 100% by mass. 15% by mass or less, preferably 13% by mass or less, more preferably 10% by mass or less. (A) By setting the content of the glycidylamine type epoxy resin within such a range, the heat resistance can be improved, and the coefficient of linear thermal expansion (CTE) can be lowered. As a result, it is possible to suppress warpage. Further, by setting the content of (A) the glycidylamine type epoxy resin within the range, it is possible to suppress cracks in the cured product of the encapsulating resin composition.

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

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

<(B) Glycidyl ester type epoxy resin>
The encapsulating resin composition contains a glycidyl ester type epoxy resin as the component (B). By including the glycidyl ester type epoxy resin in the encapsulating resin composition, the elastic modulus of the cured product of the encapsulating resin composition can be reduced, and warping can be suppressed.

(B) As the glycidyl ester type epoxy resin, an epoxy resin in which a glycidyl group is directly bonded to an ester bond can be used. Among them, from the viewpoint of further reducing the elastic modulus of the cured product of the encapsulating resin composition and further suppressing warpage, it is preferably a bifunctional or trifunctional glycidyl ester type epoxy resin, and a bifunctional glycidyl ester type epoxy resin. Epoxy resin is more preferred. For example, a bifunctional glycidyl ester type epoxy resin represents a glycidyl ester type epoxy resin having two epoxy groups in the molecule.

(B) Glycidyl ester-type epoxy resins are dimer acid-modified glycidyl ester-type epoxy resins and phthalate diglycidyl ester-type epoxy resins from the viewpoint of further reducing the elastic modulus of the cured product of the encapsulating resin composition and further suppressing warpage. Epoxy resins, diglycidyl hexahydrophthalate type epoxy resins, diglycidyl terephthalate type epoxy resins, diglycidyl isophthalate type epoxy resins, and various isomers thereof are preferred.

（式（Ｂ）中、Ｒ^２１、及びＲ^２２はそれぞれ独立にグリシジル基、又はビスフェノールＡ型ジグリシジルエーテル構造を有する基を表す。ｎ１～ｎ４はそれぞれ独立に３～９の整数を表す。） Among these, dimer acid-modified glycidyl ester-type epoxy resins are preferable as the glycidyl ester-type epoxy resin (B) from the viewpoint of achieving the desired effects of the present invention. The dimer acid-modified glycidyl ester type epoxy resin is preferably represented by, for example, the following formula (B).

(In formula (B), R ²¹ and R ²² each independently represent a glycidyl group or a group having a bisphenol A-type diglycidyl ether structure. n1 to n4 each independently represent an integer of 3 to 9.)

R ²¹ and R ²² each independently represent a glycidyl group or a group having a bisphenol A type diglycidyl ether structure, preferably a glycidyl group.

n1 represents an integer of 3 to 9, preferably an integer of 4 to 8, more preferably 5 to 7, and particularly preferably 7. n2 represents an integer of 3 to 9, preferably an integer of 5 to 9, more preferably 7 or 8, and particularly preferably 8. n3 represents an integer of 3 to 9, preferably an integer of 4 to 8, more preferably 6 or 7, and particularly preferably 6. n4 represents an integer of 3 to 9, preferably an integer of 4 to 8, more preferably 5 or 6, and particularly preferably 5.

(B) Glycidyl ester type epoxy resin may be a commercially available product, for example, "JER871" and "JER872" manufactured by Mitsubishi Chemical Corporation, "YD-171" and "YD-172" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ”, “EX-721” manufactured by Nagase ChemteX Co., Ltd., and the like.

(B) Glycidyl ester type epoxy resins may be used singly or in combination of two or more at any ratio.

(B) The epoxy equivalent of the glycidyl ester type epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product of the encapsulating resin composition is sufficient, and a sealing layer with a small surface roughness can be obtained. In addition, the epoxy equivalent can be measured by the same method as the epoxy equivalent in (A) the glycidylamine type epoxy resin.

(B) The weight average molecular weight of the glycidyl ester type epoxy resin is preferably 100-5000, more preferably 250-3000, still more preferably 400-1500. (B) The weight average molecular weight of the glycidyl ester type epoxy resin is the weight average molecular weight measured in the same manner as the weight average molecular weight of the (A) glycidyl amine type epoxy resin.

(B) The content of the glycidyl ester type epoxy resin can reduce the elastic modulus of the cured product of the sealing resin composition, and from the viewpoint of suppressing warpage, the non-volatile component in the resin composition is 100% by mass. , it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass or more. From the viewpoint of reducing the coefficient of linear thermal expansion, the upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

The encapsulating resin composition contains (A) a glycidylamine type epoxy resin and (B) a glycidyl ester type epoxy resin in a well-balanced manner so that the cured product of the encapsulating resin composition has an elastic modulus and a linear thermal expansion coefficient of can be reduced, and as a result, it is possible to suppress warpage. Therefore, when the non-volatile component in the encapsulating resin composition is 100% by mass, the content of the component (A) is a1, and the non-volatile component in the encapsulating resin composition is 100% by mass ( When the content of component B) is b1, a1/b1 is preferably 0.6 or more, more preferably 1 or more, still more preferably 1.5 or more, 2 or more, and preferably 30 or less, more preferably is 20 or less, more preferably 10 or less, 8 or less, or 5 or less.

Since the encapsulating resin composition contains a predetermined amount of (A) the glycidylamine type epoxy resin, the thermal cycle test resistance of the cured product is improved, and the coefficient of linear thermal expansion of the cured product can be lowered. . Moreover, since the encapsulating resin composition also contains (B) a glycidyl ester type epoxy resin, it is possible to lower the elastic modulus of the cured product. The present inventors have found that warping of the cured product can be suppressed by lowering both the coefficient of linear thermal expansion and the modulus of elasticity. It has been known for some time that the combined use of specific epoxy resins such as components (A) and (B) improves the thermal cycle test resistance of the cured product and suppresses the warpage of the cured product. This is new knowledge that is not available.

<(C) Curing agent>
The encapsulating resin composition contains a curing agent as the (C) component. (C) Curing agent usually has a function of curing the encapsulating resin composition by reacting with epoxy resins such as component (A), component (B), and component (E) to be described later. (C) Curing agents may be used singly or in combination of two or more at any ratio.

As the curing agent (C), a compound capable of reacting with the epoxy resin to cure the resin composition can be used. Ester-based curing agents, cyanate ester-based curing agents, benzoxazine-based curing agents, carbodiimide-based curing agents, and the like are included. Among them, an amine-based curing agent is preferred because it is capable of reacting at a low temperature and suppresses warping of a cured product of the encapsulating resin composition.

Amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′. -diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 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, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents may be used. Kayahard AS", Mitsubishi Chemical's "Epicure W", and the like.

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid.

Phenolic curing agents include curing agents having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) per molecule. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferred. Moreover, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure is preferable. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic 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 phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Kasei; "NHN", "CBN", "GPH"; Nippon Steel & Sumikin Chemical Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN -495", "SN-495V", "SN-375", "SN-395"; DIC's "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054 ”, “LA-1356”, “LA-3018”, “LA-3018-50P”, “EXB-9500”, “HPC-9500”, “KA-1160”, “KA-1163”, “KA-1165 ; "GDP-6115L", "GDP-6115H", "ELPC75" manufactured by Gunei Chemical Co., Ltd.;

Active ester curing agents include curing agents having one or more active ester groups in one molecule. Among them, active ester curing agents include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like, and have two or more ester groups per molecule with high reaction activity. Preferred are compounds having The active ester 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. .

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

Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Preferred specific examples of the active ester 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 phenol novolac, and a benzoylated phenol novolac. active ester compounds containing Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a bivalent structure consisting of phenylene-dicyclopentylene-phenylene.

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

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc.; prepolymers obtained by partially triazinizing these cyanate resins; and the like. Specific examples of cyanate ester curing agents include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both phenol novolac type polyfunctional cyanate ester resins); "ULL-950S" (polyfunctional cyanate ester resin); BA230", "BA230S75" (a 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., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.

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

From the viewpoint of suppressing warpage, the content of the curing agent (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass when the non-volatile components in the sealing resin composition are 100% by mass. % or more, more preferably 0.3 mass % or more, preferably 3 mass % or less, more preferably 2 mass % or less, and even more preferably 1 mass % or less.

When the number of epoxy groups in component (A) and component (B) is 1, the number of active groups in curing agent (C) is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. is preferably 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 the sum of all the values obtained by dividing the mass of the non-volatile components of the components (A) and (B) present in the encapsulating resin composition by the epoxy equivalent. be. In addition, "(C) the number of active groups of the curing agent" is the sum of all the values obtained by dividing the mass of the non-volatile components of the (C) curing agent present in the sealing resin composition by the active group equivalent. . When the number of active groups of the curing agent (C) is within the above range when the number of epoxy groups of the components (A) and (B) is 1, the desired effect of the present invention can be remarkably obtained. The moisture resistance of the cured product of the resin composition layer is further improved.

<(D) Inorganic filler>
The encapsulating resin composition contains an inorganic filler as the component (D). (D) By using an inorganic filler, the linear thermal expansion coefficient of the cured product of the encapsulating resin composition can be reduced, and warpage can be suppressed.

(D) An inorganic compound is used as the material of the inorganic filler. (D) Examples of inorganic filler materials 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica or alumina is particularly preferred from the viewpoint of significantly obtaining the desired effect of the present invention. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. (D) The inorganic filler may be used singly or in combination of two or more at any ratio.

(D) The inorganic filler is usually contained in the encapsulating resin composition in the form of particles. (D) The average particle size of the inorganic filler is preferably 0.1 µm or more, more preferably 0.2 µm or more, and particularly preferably 0.3 µm or more, 0.4 µm or more, 0.5 µm or more, or 1.0 µm or more. , preferably 10 μm or less, more preferably 8.0 μm or less, and particularly preferably 7.0 μm or less. When the average particle diameter of the (D) inorganic filler is within the above range, the fillability of the (D) inorganic filler in the sealing resin composition is enhanced, and the desired effect of the present invention can be remarkably obtained. can.

(D) The average particle size of particles such as inorganic fillers can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, a particle size distribution of particles can be prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring apparatus, and an average particle size can be measured as a median size from the particle size distribution. As the measurement sample, particles dispersed in a solvent such as water by ultrasonic waves can be preferably used. "LA-500" manufactured by Horiba Ltd. can be used as the laser diffraction scattering particle size distribution analyzer.

Examples of the inorganic filler (D) as described above include, for example, "ST7030-20" manufactured by Nippon Steel & Sumikin Materials; "MSS-6" and "AC-5V" manufactured by Tatsumori; SP60-05”, “SP507-05”; Admatechs “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; Denka “UFP-30”, “SFP-130MC”, “FB -7SDC", "FB-5SDC", "FB-3SDC"; Tokuyama "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; Admatechs "SC2500SQ", "SO -C4”, “SO-C2”, “SO-C1”, “FE9” and the like.

(D) The inorganic filler is preferably surface-treated with an appropriate surface-treating agent. The surface treatment can enhance the moisture resistance and dispersibility of (D) the inorganic filler. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanates. system coupling agents, and the like.

Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd. "KBM22" (dimethyldimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxy silane), Shin-Etsu Chemical Co., Ltd. "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), and the like. Among them, nitrogen atom-containing silane coupling agents are preferred, aminosilane-based coupling agents containing a phenyl group are more preferred, and N-phenyl-3-aminoalkyltrimethoxysilane is even more preferred. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D) inorganic filler. (D) The amount of carbon per unit surface area of the 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 (D) 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 form of a sheet, 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 less than or equal to 0.5 mg/m ² .

The amount of carbon per unit surface area of the (D) inorganic filler is measured after the surface-treated (D) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). , can be measured. Specifically, a sufficient amount of methyl ethyl ketone and (D) an 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 liquid and drying the solid content, the amount of carbon per unit surface area of the (D) inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

(D) 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 effects of the present invention. be. Although there is no particular upper limit, it 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 (D) inorganic filler in the resin composition is preferably 80% by mass or more, more preferably 81% by mass or more, and still more preferably 82% by mass with respect to 100% by mass of non-volatile components in the resin composition. or more, preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 91% by mass or less. (D) When the amount of the inorganic filler is within the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the coefficient of linear thermal expansion of the encapsulating resin composition can be effectively lowered. can be done.

<(E) Epoxy resin>
The encapsulating resin composition may contain an epoxy resin as the (E) component. However, (E) epoxy resin excludes (A) glycidylamine type epoxy resin and (B) glycidyl ester type epoxy resin.

(E) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins. 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 resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, alicyclic epoxy resins having an ester skeleton, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and the like. Epoxy resins may be used singly or in combination of two or more.

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

(E) As the epoxy resin, a liquid epoxy resin may be used, a solid epoxy resin may be used, or a combination of a liquid epoxy resin and a solid epoxy resin may be used. Among them, it is preferable to use a liquid epoxy resin as (E) the epoxy resin from the viewpoint of reducing the viscosity of the encapsulating resin composition.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, Preferred are cyclohexanedimethanol-type epoxy resins, aliphatic epoxy resins, and epoxy resins having a butadiene structure, and more preferred are bisphenol A-type epoxy resins and alicyclic epoxy resins having an ester skeleton.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "EXA-850CRP" (bisphenol A type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "JER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YED-216D" (aliphatic epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059" (bisphenol A type epoxy resin and bisphenol F type epoxy resin mixture); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resin); "Celoxide 2021P" manufactured by Daicel Corporation (alicyclic epoxy resin having an ester skeleton ); "PB-3600" (an epoxy resin having a butadiene structure) manufactured by Daicel; These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, 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, bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF type epoxy resins and naphthylene ether type epoxy resins are more preferred.

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

(E) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio by mass (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:0.1 to 1:0.1. :15, more preferably 1:0.3 to 1:10, particularly preferably 1:0.6 to 1:8. By keeping the ratio of the liquid epoxy resin to the solid epoxy resin within such a range, usually, when used in the form of a resin sheet, moderate adhesiveness is provided. In addition, when used in the form of a resin sheet, sufficient flexibility is usually obtained, and handleability is improved. Furthermore, usually, a cured product having sufficient breaking strength can be obtained.

(E) The weight average molecular weight of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500, from the viewpoint of significantly obtaining the desired effects of the present invention.

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

When (E) an epoxy resin is included, the content of the (E) epoxy resin is preferably 1% by mass or more, more preferably 2% by mass or more, based on 100% by mass of non-volatile components in the resin composition for sealing. , more preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. By setting the amount of (E) the epoxy resin within the above range, the mechanical strength and insulation reliability of the cured product of the encapsulating resin composition can be enhanced.

<(F) Curing accelerator>
The encapsulating resin composition may contain (F) a curing accelerator as the (F) component. By using (F) a curing accelerator, curing can be accelerated when curing the encapsulating resin composition.

(F) Curing accelerators include, for example, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metallic curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators and metallic curing accelerators are more preferable. The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5,4,0)-undecene, 4-pyrrolidinopyridine and the like. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-undecylimidazolyl-(1′)]-ethyl-s-triazine, 2, 4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-methylimidazolyl-(1′)] -ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and imidazole compounds and epoxy resins and adducts of Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation; "2E4MZ" manufactured by Shikoku Kasei Co., Ltd.;

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like. Among them, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the encapsulating resin composition contains (F) a curing accelerator, the content of (F) the curing accelerator is a non-volatile content in the encapsulating resin composition from the viewpoint of significantly obtaining the desired effects of the present invention. When the component is 100% by mass, it is preferably 0.01% by mass, more preferably 0.03% by mass, still more preferably 0.05% by mass, preferably 3% by mass, more preferably 1.5% by mass. , and more preferably 1% by mass.

<(G) Optional Additives>
The encapsulating resin composition may further contain optional additives as optional components in addition to the components described above. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thermoplastic resins; thickeners; antifoaming agents; leveling agents; flame retardants; and other resin additives. One type of these additives may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Although the above-described encapsulating resin composition may contain a solvent as necessary, it is preferably a solventless encapsulating resin composition that does not substantially contain a solvent. Thus, even if the encapsulating resin composition does not contain a solvent, it can be fluidized when it is molded using a compression molding method, and excellent compression moldability can be achieved. Therefore, this encapsulating resin composition can be used as a solventless resin composition. The expression "substantially free of solvent" means, for example, that the solvent content is 1% by mass or less with respect to the entire solventless resin composition.

[Method for producing encapsulating resin composition]
The encapsulating resin composition can be produced, for example, by a method in which the ingredients are stirred using a stirring device such as a rotary mixer.

[Characteristics of encapsulating resin composition]
A cured product having a low elastic modulus at 25° C. can be obtained from the sealing resin composition described above. Therefore, by using this encapsulating resin composition, a sealing layer and an insulating layer having a low elastic modulus can be obtained. For example, using the sealing resin composition described above, a test piece is produced by the method described in Examples, and the elastic modulus of the test piece is measured at 25°C. In this case, the obtained elastic modulus at 25° C. is usually 20 GPa or less, preferably 16 GPa or less, more preferably 13 GPa or less. There is no particular limit to the degree of adjustment, and it can usually be 0.1 GPa or more.

Moreover, according to the resin composition for sealing mentioned above, the hardened|cured material with a low coefficient of linear thermal expansion (CTE) can be obtained. Therefore, by using this encapsulating resin composition, a sealing layer and an insulating layer having a low coefficient of linear thermal expansion can be obtained. For example, using the sealing resin composition described above, a test piece is produced by the method described in Examples, and the coefficient of linear thermal expansion of the test piece is measured. In this case, the linear thermal expansion coefficient obtained is usually 15 ppm/°C or less, preferably 13 ppm/°C or less, more preferably 12 ppm/°C or less. There is no particular lower limit, and it is usually 0 ppm/°C, preferably 1 ppm/°C or more.

Moreover, according to the sealing resin composition described above, it is possible to obtain a layer of a cured product capable of suppressing warpage. Therefore, by using this encapsulating resin composition, it is possible to obtain a sealing layer and an insulating layer capable of suppressing warping of a circuit board and a semiconductor chip package. For example, using the sealing resin composition described above, a cured product layer of the sealing resin composition is formed on a 12-inch silicon wafer by the method described in the Examples to prepare a sample substrate. In this case, the amount of warp measured by the method described in the examples at 25° C. can be usually less than 3 mm, preferably less than 2 mm.

Moreover, the above-described encapsulating resin composition can provide a cured product that is excellent in high adhesion even after repeated heating and cooling, that is, excellent in thermal cycle test resistance. Therefore, by using this encapsulating resin composition, it is possible to obtain an encapsulating layer and an insulating layer that are excellent in thermal cycle test resistance. For example, using the sealing resin composition described above, a resin wafer is produced by forming a cured product layer of the sealing resin composition on a 12-inch silicon wafer on which a silicon chip is mounted. In this case, a thermal cycle test in which 1000 cycles of a cycle of 30 minutes of treatment at -55 ° C. and 30 minutes of treatment at 120 ° C. is measured by the method described in the example, usually , no delamination occurs at the interface between the silicon chip and the cured material layer.

In addition, the sealing resin composition described above usually exhibits a characteristic of low viscosity. Therefore, by using this encapsulating resin composition, it is possible to obtain excellent handleability when performing compression molding using a compression molding machine. For example, using an RE80 type viscometer (0.2 to 0.3 ml of the sealing resin composition to be measured, measurement 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 encapsulating resin composition can be usually 600 Pa·s or less, preferably 550 Pa·s or less. There is no particular upper limit, and it can usually be 0.1 Pa·s or more.

In addition, the above-described encapsulating resin composition usually exhibits a low minimum melt viscosity from 60°C to 200°C. Therefore, by using this encapsulating resin composition, excellent embedding properties can be obtained when manufacturing a circuit board or the like. For example, using a dynamic viscoelasticity measuring device (1.2 to 1.3 g of the sealing resin composition to be measured, using a parallel plate with a diameter of 18 mm), the temperature rise rate from the starting temperature of 60 ° C. to 200 ° C. The temperature is raised at a rate of 5° C./min, and the dynamic viscoelastic modulus is measured under the measurement conditions of a measurement temperature interval of 2.5° C., a frequency of 1 Hz, and a strain of 1 deg. In this case, the minimum melt viscosity of the encapsulating resin composition can be usually 400 poise or less, preferably 300 poise or less, more preferably 200 poise or less. There is no particular upper limit, and it can be usually 50 poise or more, preferably 80 poise or more, and more preferably 100 poise or more.

The sealing resin composition described above is excellent in compression moldability. Therefore, when a resin composition layer is formed on a circuit board or a semiconductor chip by compression molding, it is possible to fill every corner with the sealing resin composition. Therefore, by curing the resin composition layer, a sealing layer having excellent sealing reliability and an insulating layer having excellent insulation reliability can be obtained.

The encapsulating resin composition may be liquid or solid, but is preferably liquid at the time of molding. For example, a sealing resin composition that is liquid at normal temperature (e.g., 20° C.) may be molded by compression molding at normal temperature without special temperature adjustment, and may be heated to an appropriate temperature and compression molded. You may perform molding by a method. Alternatively, a sealing resin composition that is liquid at room temperature may be filled in a cartridge, discharged from the cartridge, and then molded by a compression molding method. good.

In addition, since the sealing resin composition, which is solid at room temperature, can be made liquid by adjusting the temperature to a higher temperature (for example, 130 ° C.), compression molding can be performed by appropriate temperature adjustment such as heating. can be molded by The above sealing resin composition can usually become liquid at an appropriate temperature without containing a solvent, and can be used, for example, as a liquid sealing material. Here, the term "liquid" refers to a substance having a viscosity of less than 1500 Pa·s as measured by the method described in [Measurement of Viscosity] below.

Since the encapsulating resin composition has the properties described above, it can be suitably used as a resin composition for encapsulating electronic devices such as organic EL devices and semiconductors. (semiconductor encapsulation resin composition), preferably as a resin composition for encapsulating a semiconductor chip (semiconductor chip encapsulation resin composition). Moreover, the resin composition for sealing can be used as a resin composition for insulating layers other than the use for sealing. For example, the encapsulating resin composition includes a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package), and a circuit board (including a printed wiring board). ) (resin composition for insulating layers of circuit boards).

Examples of semiconductor chip packages 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), Fan-in type PLPs can be mentioned.

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

Furthermore, the resin composition for encapsulation has a wide range of applications in which the resin composition for encapsulation is used, such as resin sheets, sheet-like laminate materials such as prepreg, solder resists, die bonding materials, hole-filling resins, and component-embedding resins. 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 encapsulating resin composition of the present invention, and is usually formed of the encapsulating resin composition.

The thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, even more preferably 500 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, or 200 μm or less from the viewpoint of thinning. 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, or 10 µm or more.

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, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). Polycarbonate (hereinafter sometimes abbreviated as "PC"); Acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); Cyclic polyolefins; Triacetyl cellulose (hereinafter polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; polyimide; Among them, 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. Among them, 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 other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, antistatic treatment, or the like on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include alkyd resin release agents such as “SK-1”, “AL-5” and “AL-7” manufactured by Lintec. Examples of the release layer-attached support include "Lumirror T60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin Limited; and "Unipeel" manufactured by Unitika.

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 release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within 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. Moreover, if necessary, the resin composition for sealing may be dissolved in an organic solvent to prepare a resin varnish, and this resin varnish may be applied to manufacture 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 composition layer is usually formed by drying the resin varnish after application.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols 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; The organic solvent may be used singly 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 varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes The resin composition layer can be formed.

The resin sheet may contain arbitrary layers other than the support and the resin composition layer, if necessary. For example, in the resin sheet, a protective film conforming 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 from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. 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 wound into a roll 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-described sealing resin composition is used as a sealing layer for semiconductor chips and the like on a circuit board as described later. It may be formed by an object. However, the insulating layer may be formed of a material other than the cured resin composition for sealing described above.
(1) A step of forming a resin composition layer on a substrate.
(2) A step of thermosetting the resin composition layer to form an insulating layer.

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

Also, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be referred to as a "wiring layer-attached base material" as appropriate. The conductor material contained in the conductor layer is, 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 alloys include alloys of two or more metals selected from the above group (eg, nickel-chromium alloys, copper-nickel alloys and copper-titanium alloys). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as single metals; and nickel-chromium alloys as alloys , a copper-nickel alloy, and a copper-titanium alloy; are preferred. Among them, single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys; are more preferred, and single metals of copper are particularly preferred.

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 preferably 10/10 μm or less. 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 need not be the same throughout the conductor layer. The minimum pitch of the conductor layers may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

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

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

After preparing the substrate, a resin composition layer is formed on the substrate. When a conductor layer is formed on the surface of the substrate, the resin composition layer is preferably formed so that the conductor layer is embedded in the resin composition layer.

Formation of the resin composition layer is performed, for example, by laminating a resin sheet and a substrate. This lamination can be performed, for example, by bonding the resin composition layer to the substrate by thermocompression bonding the resin sheet to the substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the substrate (hereinafter sometimes referred to as "thermocompression member") include heated metal plates (such as SUS end plates) and metal rolls (such as SUS rolls). be done. Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the substrate.

Lamination of the base material and the resin sheet may be carried out, for example, by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C. The thermocompression 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-pressing 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 of 13 hPa or less.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Lamination and smoothing may be performed continuously using a vacuum laminator.

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

After forming the resin composition layer on the substrate, the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions for the resin composition layer vary depending on the type of 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 in the range of 170°C to 200°C). range), and 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).

Prior to thermal curing of the resin composition layer, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually heated 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 more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

A circuit board having an insulating layer can be manufactured in the manner described above. Moreover, the method for manufacturing the 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 heat curing of the resin composition layer, or may be peeled off after heat curing of the resin composition layer.

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

The method of manufacturing the circuit board may include, for example, the step (3) of connecting the conductor layers between the layers, that is, the step of drilling holes in the insulating layers. As a result, holes such as via holes and through holes can be formed in the insulating layer. Examples of methods for forming via holes 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 step (3), 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 smear in the via hole. This process is sometimes called a desmear process. For example, when the conductive layer is formed on the insulating layer by a plating process, the via holes may be subjected to a wet desmear treatment. Further, when the conductor layer is formed on the insulating layer by a sputtering process, a dry desmear process such as a plasma treatment process may be performed. Furthermore, the insulating layer may be roughened by a desmear process.

Further, the insulating layer may be roughened before forming the conductor layer 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 dry or wet roughening treatment may be performed. Examples of dry roughening treatment include plasma treatment and the like. Moreover, examples of wet roughening treatment include a method in which swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid are performed in this order.

After forming the via holes, a conductor layer is formed on the insulating layer. By forming a 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 electrically connected to each other, thereby performing interlayer connection. Methods for forming the conductor layer include, for example, plating, sputtering, vapor deposition, etc. Among them, plating is 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. Moreover, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Moreover, this conductor layer may have a single layer structure, or may have a multi-layer structure including two or more layers of different kinds of materials.

An example embodiment of forming a conductor layer on an insulating layer will now 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 portion of the plating seed layer corresponding to a desired wiring pattern. After forming an electrolytic plating layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by a treatment such as etching to form a conductor layer having a desired wiring pattern. The dry film used for forming the mask pattern when forming the conductor layer is the same as the dry film described above.

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

[Semiconductor chip package]
A semiconductor chip package according to a first embodiment of the present invention includes the circuit board described above, a semiconductor chip mounted on the circuit board, and a cured product of the sealing resin composition of the present invention that seals the semiconductor chip. including. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

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

Any condition that allows conductor connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board can be adopted as the bonding condition of the circuit board and the semiconductor chip. For example, conditions used in flip-chip mounting of semiconductor chips can be employed. Alternatively, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

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

Another example of the bonding method is a method of reflowing and bonding a semiconductor chip to a circuit board. The reflow conditions may range from 120.degree. C. to 300.degree.

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

A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor chip and a cured product of the sealing resin composition for sealing the semiconductor chip. As a semiconductor chip package according to the second embodiment, for example, a fan-out type WLP can be used.

A method for manufacturing such a semiconductor chip package includes:
(A) a step of laminating a temporary fixing film on a substrate;
(B) temporarily fixing the semiconductor chip on the temporary fixing film;
(C) forming a sealing layer on the semiconductor chip;
(D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed;
(F) forming a rewiring layer as a conductor layer on the rewiring forming layer;
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method for manufacturing the semiconductor chip package includes:
(H) A step of dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to individualize them.

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

Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel and cold-rolled steel plate (SPCC); A heat-cured substrate; a substrate made of bismaleimide triazine resin such as BT resin; and the like.

Any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used for the temporary fixing film. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

(Step (B))
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 using a device such as a flip chip bonder, a die bonder, or the like. The layout and the number of semiconductor chips to be arranged can be appropriately set according to the shape and size of the temporary fixing film, the target production volume of the semiconductor package, and the like. For example, the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and temporarily fixed.

(Step (C))
Step (C) is a step of forming a sealing layer on the semiconductor chip. The encapsulating layer is formed from a cured product of the encapsulating resin composition described above. The sealing layer is usually formed by a method including the steps of forming a sealing resin composition layer on the semiconductor chip and thermally curing the resin composition layer to form the sealing layer.

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

A specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. In addition, 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 encapsulating resin composition is attached to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped, and heat and pressure are applied to the encapsulating resin composition for compression molding.

Further, the specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. A sealing resin composition is placed on the lower mold. Also, 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 clamped so that the sealing resin composition placed on the lower mold is in contact with the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

Molding conditions vary depending on the composition of the encapsulating resin composition, and appropriate conditions can be adopted so as to achieve good encapsulation. For example, the temperature of the mold during molding is preferably a temperature at which the encapsulating 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. , preferably 200° C. or lower, more preferably 170° C. or lower, particularly preferably 150° C. or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. After formation of the resin composition layer, the mold is usually removed. The mold may be removed before or after heat curing of the resin composition layer.

The compression molding method may be performed by discharging the sealing resin composition filled in the cartridge into a lower mold. The molding conditions after forming the resin composition layer are the same as the conditions for compression molding.

The resin composition layer may be formed by laminating a resin sheet and a semiconductor chip. For example, the resin composition layer can be formed on the semiconductor chip by thermocompression bonding the resin composition layer of the resin sheet and the semiconductor chip. The lamination of the resin sheet and the semiconductor chip can be carried out in the same manner as the lamination of the resin sheet and the base material in the manufacturing method of the circuit board, usually using the semiconductor chip instead of the base material.

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 resin composition for sealing. The thermosetting conditions for the resin composition layer may be the same as the thermosetting conditions for the resin composition layer in the circuit board manufacturing method. Furthermore, before thermally curing the resin composition layer, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. As the processing conditions for this preheating treatment, the same conditions as those for the preheating treatment in the circuit board manufacturing method may be employed.

(Step (D))
Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip. As for the peeling method, it is desirable to employ 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. Moreover, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive strength of the temporary fixing film and peel it off can be used.

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

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

Any insulating material can be used as the material of the rewiring formation layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness in manufacturing semiconductor chip packages. Moreover, you may use the resin composition for sealing of this invention as this thermosetting resin.

After the rewiring formation layer is formed, via holes may be formed in the rewiring formation layer for interlayer connection between the semiconductor chip and the rewiring layer.

In the method of forming a via hole when the material of the rewiring layer is a photosensitive resin, the surface of the rewiring layer is usually irradiated with an active energy ray through a mask pattern to irradiate the rewiring layer in the irradiated portion with light. Harden. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. The exposure method includes, for example, a contact exposure method in which the mask pattern is brought into close contact with the rewiring layer and exposed, and a non-contact exposure method in which the mask pattern is not brought into close contact with the rewiring layer and is exposed using parallel light rays. is mentioned.

After the rewiring layer is photo-cured, the rewiring layer is developed to remove the unexposed portions to form via holes. The development may be either wet development or dry development. The development method includes, for example, a dipping 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.

When the material of the rewiring formation layer is a thermosetting resin, the method of forming via holes includes, for example, laser irradiation, etching, mechanical drilling, and the like. Among them, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide laser, a UV-YAG laser, an excimer laser, or the like.

Although the shape of the via hole is not particularly limited, it is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, still more 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 layer.

(Step (F))
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 can be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing the circuit board. Alternatively, the steps (E) and (F) may be repeated to alternately build up the rewiring layers and the rewiring formation layers (build-up).

(Step (G))
Step (G) is a step of forming a solder resist layer on the rewiring layer. Any insulating material can be used as the material of the solder resist layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness in manufacturing semiconductor chip packages. Moreover, you may use the resin composition for sealing of this invention as a thermosetting resin.

Moreover, in the step (G), a bumping process for forming bumps may be performed as necessary. Bumping can be performed by a method such as solder balls or solder plating. Formation of via holes in the bumping process can be performed in the same manner as in step (E).

The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces. The method of dicing the 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, the semiconductor chip package of the second embodiment, in which the rewiring formation layer or the solder resist layer is formed from the cured product of the resin composition of the present invention. is.

[Semiconductor device]
Examples of semiconductor devices on which the above-described semiconductor chip package is mounted include electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g. , motorcycles, automobiles, trains, ships, aircraft, etc.).

EXAMPLES 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 amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, unless otherwise specified, the operations described below were performed in an environment of normal temperature and normal pressure.

<Inorganic filler used>
Silica A: average particle diameter 6.0 μm, maximum cut diameter 20 μm, specific surface area 4.8 m ² /g, spherical silica treated with KBM573 (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) .
Silica B: spherical silica treated with KBM403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) with an average particle diameter of 4.8 μm, a maximum cut diameter of 20 μm, a specific surface area of 3.9 m ² /g.
Alumina A: average particle diameter 4.8 μm, maximum cut diameter 24 μm, specific surface area 2.7 m ² /g, spherical alumina treated with KBM573 (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) .

[Preparation of encapsulating resin composition]
<Example 1>
Glycidylamine type epoxy resin (ADEKA "EP3980S", epoxy equivalent 115 g / eq.) 3 parts, glycidylamine type epoxy resin (Mitsubishi Chemical "630", epoxy equivalent 95 g / eq.) 6 parts, glycidyl dimerate Ester (manufactured by Mitsubishi Chemical Corporation "JER871", epoxy equivalent 412 g / eq.) 2 parts, bisphenol A type epoxy resin (DIC Corporation "EXA-850CRP", epoxy equivalent 170 to 175 g / eq.) 4 parts, amine curing Agent (“KAYABOND C-200S” manufactured by Nippon Kayaku Co., Ltd.) 0.5 parts, alumina A 95 parts, and curing accelerator (“2E4MZ” manufactured by Shikoku Kasei Co., Ltd.) 0.4 parts are uniformly dispersed using a mixer. , to obtain a sealing resin composition.

"EP3980S", "630" and "KAYABOND C-200S" are represented by the following structural formulas.

<Example 2>
In Example 1, 3 parts of a glycidylamine type epoxy resin ("EP3980S" manufactured by ADEKA, epoxy equivalent 115 g/eq.) was added to an alicyclic epoxy resin ("CEL2021P" manufactured by Daicel, epoxy equivalent 136 g/eq.). 3 parts and 95 parts of Alumina A was changed to 83 parts of Silica A. A sealing resin composition was obtained in the same manner as in Example 1 except for the above matters.

"CEL2021P" is represented by the following structural formula.

<Example 3>
In Example 1, 95 parts of Alumina A were replaced with 83 parts of Silica A. A sealing resin composition was obtained in the same manner as in Example 1 except for the above matters.

<Example 4>
In Example 1, 95 parts of Alumina A were replaced with 83 parts of Silica B. A sealing resin composition was obtained in the same manner as in Example 1 except for the above matters.

<Comparative Example 1>
Glycidylamine type epoxy resin (ADEKA "EP3980S", epoxy equivalent 115 g / eq.) 6 parts, dimer acid glycidyl ester (Mitsubishi Chemical Corporation "JER871", epoxy equivalent 412 g / eq.) 0.5 parts, glycidylamine Type epoxy resin (manufactured by Mitsubishi Chemical Corporation "630", epoxy equivalent 95 g / eq.) 10 parts, amine curing agent (manufactured by Nippon Kayaku Co., Ltd. "KAYABOND C-200S") 0.5 parts, silica B 85 parts, curing 0.4 part of an accelerator (“2E4MZ” manufactured by Shikoku Kasei Co., Ltd.) was uniformly dispersed using a mixer to obtain a sealing resin composition.

<Comparative Example 2>
Glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation "630", epoxy equivalent 95 g / eq.) 2 parts, dimer acid glycidyl ester (manufactured by Mitsubishi Chemical Corporation "JER871", epoxy equivalent 412 g / eq.) 0.5 parts, bisphenol A-type epoxy resin (manufactured by DIC "EXA-850CRP", epoxy equivalent 170 to 175 g / eq.) 13 parts, amine curing agent (manufactured by Nippon Kayaku Co., Ltd. "KAYABOND C-200S") 0.5 parts, silica B 85 parts and 0.4 parts of a curing accelerator (“2E4MZ” manufactured by Shikoku Kasei Co., Ltd.) were uniformly dispersed using a mixer to obtain a sealing resin composition.

<Comparative Example 3>
In Example 2, 2 parts of dimer acid glycidyl ester ("JER871" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 412 g/eq.) was not added. A sealing resin composition was obtained in the same manner as in Example 2 except for the above matters.

[Measurement of elastic modulus]
The encapsulating resin compositions produced in Examples and Comparative Examples were placed on a SUS plate whose surface had been subjected to mold release treatment, using a compression molding device (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). ) to form a resin composition layer having a thickness of 300 μm. The SUS plate was peeled off, and the resin composition layer was thermally cured by heating at 180° C. for 90 minutes to obtain a cured product layer of the sealing resin composition. This cured product layer was cut into dumbbell-shaped No. 1 specimens to obtain test pieces. The tensile strength of the test piece was measured using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd. to determine the elastic modulus at 25°C. The measurement was carried out according to JIS K7127. This operation was performed three times and the average value is shown in the table (unit: GPa).

[Measurement of coefficient of linear thermal expansion (CTE)]
The encapsulating resin compositions produced in Examples and Comparative Examples were placed on a SUS plate whose surface had been subjected to mold release treatment, using a compression molding device (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). ) to form a resin composition layer having a thickness of 300 μm. The SUS plate was peeled off, and the resin composition layer was thermally cured by heating at 180° C. for 90 minutes to obtain a cured product layer of the sealing resin composition. This cured product layer was cut to a width of 5 mm and a length of 15 mm to obtain a test piece. This test piece was subjected to thermomechanical analysis by a tensile load method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Specifically, after mounting the test piece on the thermomechanical analyzer, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5° C./min. Then, in the second measurement, the linear thermal expansion coefficient (ppm/°C) in the planar direction was calculated in the range from 25°C to 150°C.

[Evaluation of warpage]
The encapsulating resin compositions produced in Examples and Comparative Examples were compression-molded onto a 12-inch silicon wafer using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). to form a resin composition layer having a thickness of 300 μm. After that, the resin composition layer was thermally cured by heating at 180° C. for 90 minutes. As a result, a sample substrate including a silicon wafer and a cured product layer of the resin sealing resin composition was obtained. Using a shadow moire measuring device (“Thermoire AXP” manufactured by Akorometrics), the amount of warpage of the sample substrate at 25° C. was measured. The measurement was performed in accordance with JEITA EDX-7311-24 of the Japan Electronics and Information Technology Industries Association standard. Specifically, a virtual plane calculated by the method of least squares of all data of the substrate surface in the measurement area was used as a reference plane, and the difference between the minimum value and the maximum value in the direction perpendicular to the reference plane was obtained as the amount of warpage. A warpage amount of less than 2 mm was evaluated as "◯", a warpage amount of 2 mm or more and less than 3 mm was evaluated as "Δ", and a warp amount of 3 mm or more was evaluated as "x".

[Evaluation of thermal cycle test resistance]
A Thermal release tape Riva Alpha was attached to a 12-inch wafer, and a silicon chip of 1 cm×1 cm×0.3 mm was mounted thereon. The sealing resin compositions prepared in Examples and Comparative Examples were compressed using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes) so that the thickness on the chip was 100 μm. Molded. Subsequently, the encapsulating resin composition was thermally cured by heating at 150° C. for 60 minutes. A resin wafer in which silicon chips were embedded was obtained by peeling off the riba-alpha. The resulting resin wafer was treated using a small thermal shock apparatus "TSE-11" manufactured by Espec Co., Ltd., and the treatment was performed continuously at -55 ° C. for 30 minutes and at 120 ° C. for 30 minutes as one cycle. A thermal cycle test was carried out for 1000 cycles. The interface between the silicon chip and the cured encapsulating resin composition was observed by FIB, and the case where delamination did not occur was rated as "◯", and the case where delamination occurred was rated as "x".

[Viscosity measurement]
Using a syringe, 0.2 to 0.3 ml of the sealing resin composition to be measured was measured using an RE80 type viscometer (manufactured by Toki Sangyo Co., Ltd.). During the measurement, the temperature of the measurement chamber of the viscometer was controlled at 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 was measured after 120 seconds (unit: Pa·s).

[Measurement of minimum melt viscosity]
1.2 to 1.3 g of the encapsulating resin compositions prepared in Examples and Comparative Examples were measured using a parallel plate with a diameter of 18 mm using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Co., Ltd.). ”), the temperature was raised from the starting temperature of 60 ° C. to 200 ° C. at a temperature increase rate of 5 ° C./min, and the dynamic viscoelastic modulus was measured under the measurement conditions of a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, and a strain of 1 deg. was measured to calculate the lowest melt viscosity (poise).

＊表中、（Ｄ）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（Ｄ）成分の含有量を表す。

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

In Examples 1 to 4, even if the components (E) and (F) are not contained, it has been confirmed that results similar to those of the above Examples are obtained, albeit to varying degrees.

Claims (13)

(A) a glycidylamine type epoxy resin,
(B) a glycidyl ester type epoxy resin,
(C) a curing agent, and (D) an inorganic filler, a sealing resin composition containing
(B) component is a dimer acid-modified glycidyl ester type epoxy resin,
(B) a glycidyl ester type epoxy resin having an epoxy equivalent of 110 to 1000;
When the non-volatile component in the encapsulating resin composition is 100% by mass, the content of component (A) is 3% by mass or more and 15% by mass or less, and the content of component (B) is 1% by mass. The encapsulating resin composition, which is not less than 5% by mass or less. 2. The encapsulating resin composition according to claim 1, wherein component (A) is a bifunctional or trifunctional glycidylamine type epoxy resin. The content of component (A) when the nonvolatile component in the encapsulating resin composition is 100% by mass is defined as a1, and the nonvolatile component in the encapsulating resin composition is defined as 100% by mass (B). 3. The encapsulating resin composition according to claim 1, wherein a1/b1 is 0.6 or more and 10 or less, where b1 is the content of the component. The encapsulating material according to any one of claims 1 to 3, wherein the content of the component (A) is 5% by mass or more when the non-volatile component in the encapsulating resin composition is 100% by mass. Resin composition. 5. Any one of claims 1 to 4, wherein the content of component (C) is 0.1% by mass or more and 3% by mass or less when the non-volatile component in the encapsulating resin composition is 100% by mass. The encapsulating resin composition according to 1. The encapsulating resin composition according to any one of claims 1 to 5, wherein component (C) contains an amine-based curing agent. The content of component (D) 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 6. The encapsulating resin composition. The encapsulating resin composition according to any one of claims 1 to 7, wherein component (D) has an average particle size of 0.1 µm or more and 10 µm or less. The encapsulating resin composition according to any one of claims 1 to 8, wherein component (D) is silica or alumina. The encapsulating resin composition according to any one of claims 1 to 9, which is a liquid encapsulating resin composition. The encapsulating resin composition according to any one of claims 1 to 10, wherein the encapsulating resin composition has a minimum melt viscosity from 60°C to 200°C of 50 poise or more and 400 poise or less. A semiconductor chip comprising 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 11 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 11 for encapsulating the semiconductor chip.