TWI852984B - Resin composition - Google Patents

Abstract

The subject of the present invention is to provide a resin composition that can suppress the warping of a cured product and has excellent adhesion of a cured product film to a load in a vertical direction after an environmental test. The solution is a resin composition that contains (A) an epoxy resin, (B) a (meth) acrylic polymer that is liquid at 25°C, (C) a hardener, and (D) an inorganic filler, wherein the component (A) includes (A-1) a glycidylamine-type epoxy resin.

Description

Resin composition

The present invention relates to: a resin composition comprising an epoxy resin and a curing agent; a cured product of the resin composition; a resin sheet comprising the resin composition; a circuit substrate comprising the cured product; a semiconductor chip package comprising the cured product; and a semiconductor device having the semiconductor chip package.

In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has been increasing, and along with this, the insulating materials used in semiconductor chip packages in such small electronic devices are also required to have higher functionality. Such insulating layers are known to be formed by curing a resin composition (see, for example, Patent Document 1). [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2017-008312

[The problem that the invention wants to solve]

In particular, in recent years, there has been a demand for smaller semiconductor chip packages, and therefore the thickness of the insulating layer or sealing material used in the semiconductor chip package, and the silicon chip itself, has also been required to be thinner. Therefore, the development of an insulating layer that can suppress warping even with a thinner thickness is expected.

However, as the absolute amount of the resin component in the film decreases, it will be difficult to maintain the adhesion strength. In particular, for resin materials used in such applications, the adhesion strength of the film to the load in the vertical direction is important.

The subject of the present invention is to provide a resin composition that can suppress the warping of the obtained cured product and has excellent adhesion of the cured film to the load in the vertical direction after environmental testing. [Means for solving the problem]

In order to achieve the subject of the present invention, the inventors of the present invention have conducted in-depth research and found that: "By including (A-1) a glycidylamine-type epoxy resin and (B) a (meth)acrylic polymer that is liquid at 25°C in the resin composition, the warping of the cured product can be suppressed, and the cured film after environmental testing can have excellent adhesion to a load in the vertical direction." Therefore, the present invention was completed.

That is, the present invention includes the following contents. [1]. A resin composition comprising (A) an epoxy resin, (B) a (meth) acrylic polymer that is liquid at 25°C, (C) a hardener, and (D) an inorganic filler, wherein the component (A) comprises (A-1) a glycidylamine-type epoxy resin. [2]. The resin composition as described in [1] above, wherein the component (A-1) is a difunctional or trifunctional glycidylamine-type epoxy resin. [3]. The resin composition as described in [1] or [2] above, wherein the content of the component (A-1) is 20% by mass or more and 80% by mass or less, when the non-volatile components other than the component (D) in the resin composition are taken as 100% by mass. [4]. The resin composition as described in any one of [1] to [3] above, wherein the content of component (B) is 0.5% by mass or more and 20% by mass or less, based on 100% by mass of non-volatile components other than component (D) in the resin composition. [5]. The resin composition as described in any one of [1] to [4] above, wherein component (C) is a curing agent selected from the group consisting of phenolic curing agents, naphthol curing agents, acid anhydride curing agents, amine curing agents and imidazole curing agents. [6]. The resin composition as described in any one of [1] to [5] above, wherein the content of component (D) is 70% by mass or more, based on 100% by mass of all non-volatile components in the resin composition. [7]. A resin composition as described in any one of [1] to [6], which is used to form an insulating layer of a semiconductor chip package. [8]. A resin composition as described in any one of [1] to [6], which is used to form an insulating layer of a circuit board. [9]. A resin composition as described in any one of [1] to [6], which is used to seal a semiconductor chip of a semiconductor chip package. [10]. A cured product of a resin composition as described in any one of [1] to [9]. [11]. A resin sheet having a support and a resin composition layer disposed on the support, the resin composition layer comprising a resin composition as described in any one of [1] to [9]. [12]. A circuit board comprising an insulating layer formed by a cured product of a resin composition as described in any one of [1] to [9]. [13]. A semiconductor chip package comprising a circuit board as described in [12] and a semiconductor chip mounted on the circuit board. [14]. A semiconductor chip package comprising a semiconductor chip and a cured product of a resin composition as described in any one of [1] to [9] that seals the semiconductor chip. [15]. A semiconductor device comprising a semiconductor chip package as described in [13] or [14]. [Effect of the Invention]

According to the present invention, there can be provided: a resin composition capable of suppressing warping of a cured product and having excellent adhesion of a cured product film to a load in a vertical direction after an environmental test; a cured product of the resin composition; a resin sheet comprising the resin composition; a circuit substrate comprising the cured product; a semiconductor chip package comprising the cured product; and a semiconductor device having the semiconductor chip package.

[Best Mode for Carrying Out the Invention]

The present invention will be described below based on its suitable embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented within the scope of the patent application of the present invention and its equivalent.

<Resin composition> The resin composition of the present invention contains (A) epoxy resin, (B) (meth) acrylic polymer which is liquid at 25°C, (C) hardener and (D) inorganic filler. Component (A) contains (A-1) glycidylamine type epoxy resin.

By using such a resin composition, the warping of the cured product can be suppressed, and the cured film after environmental testing can have excellent adhesion to a load in a vertical direction.

The resin composition of the present invention may further include any component in addition to (A) epoxy resin, (B) (meth) acrylic polymer that is liquid at 25°C, (C) hardener, and (D) inorganic filler. As the arbitrary component, there can be mentioned (E) organic solvent and (F) other additives. The following is a detailed description of each component included in the resin composition. <(A) Epoxy resin> The resin composition of the present invention includes (A) epoxy resin.

The content of component (A) is not particularly limited, but when the non-volatile components other than component (D) in the resin composition are set to 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 35% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 92% by mass or less, more preferably 90% by mass or less, and particularly preferably 88% by mass or less from the viewpoint of significantly obtaining the desired effect of the present invention.

<(A-1) Glycidylamine type epoxy resin> Component (A) includes (A-1) glycidylamine type epoxy resin. The so-called (A-1) glycidylamine type epoxy resin means an epoxy resin having at least one glycidylamine group and/or diglycidylamine group. The glycidylamine group includes one epoxy group, and the diglycidylamine group includes two epoxy groups. By using the (A-1) glycidylamine type epoxy resin, the glass transition temperature (Tg) of the cured product of the resin composition can be increased to improve the heat resistance, and the mechanical strength and moisture resistance of the cured product can be improved.

(A-1) The glycidylamine epoxy resin is preferably a difunctional or higher glycidylamine epoxy resin having two or more epoxy groups in one molecule, and more preferably a difunctional or trifunctional glycidylamine epoxy resin having two or three epoxy groups in one molecule, from the viewpoint of obtaining a cured product having excellent heat resistance. Here, the epoxy group is not limited to those derived from a glycidylamine group or a diglycidylamine group, and may include those derived from a glycidyloxy group. When the non-volatile components of the glycidylamine type epoxy resin are taken as 100 mass %, the ratio of the difunctional or higher functional glycidylamine type epoxy resin is preferably 50 mass % or more, more preferably 60 mass % or more, and even more preferably 70 mass % or more from the viewpoint of improving the heat resistance of the cured product.

The component (A-1) preferably has one or more aromatic rings in the molecule from the viewpoint of further improving heat resistance and further reducing the coefficient of linear thermal expansion. In the present specification, the aromatic ring means an aromatic carbon ring such as a benzene ring or a naphthalene ring, or an aromatic heterocyclic ring such as a pyridine ring, a pyrrole ring, a furan ring, a thiophene ring, etc. When there are two or more aromatic rings in the molecule, the aromatic rings can be directly bonded to each other or bonded via an oxygen atom, an alkylene group, or a combination thereof.

In this specification, the so-called alkylene group means a straight chain or branched divalent aliphatic saturated hydrocarbon group. Preferably, it is an alkylene group having 1 to 10 carbon atoms, and more preferably, it is an alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, 1,1-dimethylethylene, etc., and the bonding position of these groups is not particularly limited.

In the component (A-1), the glycidylamine group and the diglycidylamine group can be directly bonded to the aromatic ring. The aromatic ring may further have other substituents in addition to the glycidylamine group and the diglycidylamine group. Here, as other substituents, there can be mentioned, for example, a group containing a monovalent epoxy group, a monovalent alkyl group, etc. As the group containing a monovalent epoxy group, there can be mentioned a glycidyloxy group, etc. As the monovalent alkyl group, there can be mentioned, for example, an alkyl group, an aryl group, etc.

In the present specification, the so-called alkyl group means a linear or branched monovalent aliphatic saturated hydrocarbon group. Preferably, it is an alkyl group having 1 to 10 carbon atoms, and more preferably, it is an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, and the like.

In the present specification, the term "aryl" means a monovalent aromatic hydrocarbon group. Preferably, the aryl group has 6 to 14 carbon atoms, and more preferably, the aryl group has 6 to 10 carbon atoms. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, biphenyl, and 2-anthryl.

The component (A-1) may be used alone or in combination of two or more.

From the viewpoint of remarkably obtaining the desired effect of the present invention, preferred examples of the component (A-1) include those represented by the following formula (A-1).

In formula (A-1), n represents an integer of 0 to 4 independently. Preferably, n is an integer of 0 to 3, more preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. In formula (A-1), m represents an integer of 1 to 3. Preferably, m is 1 or 2, and more preferably 1.

In formula (A-1), R ¹¹ independently represents a group containing a monovalent epoxide group such as a glycidyloxy group, and a monovalent alkyl group such as an alkyl group or an aryl group. When R ¹¹ is a glycidyloxy group, the R ¹¹ is preferably bonded to the para position based on the bonding site between the nitrogen atom and the benzene ring. When R ¹¹ is an alkyl group, the R ¹¹ is preferably bonded to the ortho position based on the bonding site between the nitrogen atom and the benzene ring.

In formula (A-1), R ¹² represents a hydrogen atom or a 1- to 3-valent alkyl group. Examples of the divalent alkyl group include an alkylene group and an arylene group. When m is 1, from the viewpoint of obtaining the desired effect of the present invention, R ¹² is preferably an alkylene group, and more preferably a methyl group. Furthermore, when m is 2, from the viewpoint of obtaining the desired effect of the present invention, R ¹² is preferably an alkylene group, and more preferably a methylene group.

In the present specification, the term "arylene group" means a divalent aromatic hydrocarbon group. Preferably, the arylene group has 6 to 14 carbon atoms, and more preferably, the arylene group has 6 to 10 carbon atoms. Examples of the arylene group include phenylene, naphthylene, biphenylene, etc., and the bonding position of these groups is not particularly limited.

Specific examples of the component (A-1) include "630" and "630LSD" manufactured by Mitsubishi Chemical (such as the following formula (A-2)), "EP-3980S" (such as the following formula (A-3)), "EP3950S", and "EP3950L" manufactured by ADEKA, and "ELM-100", "ELM-100H", "ELM-434", and "ELM-434L" manufactured by Sumitomo Chemical Co., Ltd. These may be used alone or in combination of two or more.

(A-1) The epoxy equivalent of the glycidylamine epoxy resin is preferably 50 to 5000 g/eq, more preferably 50 to 3000 g/eq, more preferably 60 to 2000 g/eq, and particularly preferably 70 to 1000 g/eq. By making the epoxy equivalent of the glycidylamine epoxy resin within the aforementioned range, the crosslinking density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be provided.

The weight average molecular weight (Mw) of the glycidylamine type epoxy resin (A-1) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight average molecular weight of the resin can be obtained as a polystyrene-equivalent value by measuring by gel permeation chromatography (GPC).

The content of the component (A-1) is not particularly limited, but when the non-volatile components other than the component (D) in the resin composition are set to 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less from the viewpoint of significantly obtaining the desired effect of the present invention.

The content of the component (A-1) relative to the total amount of the component (A) is not particularly limited, but when the component (A) in the resin composition is set to 100 mass%, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 10 mass% or more, more preferably 20 mass% or more, more preferably 30 mass% or more, and particularly preferably 40 mass% or more. The upper limit is not particularly limited, and can be, for example, 100 mass% or less, 90 mass% or less, 80 mass% or less, 70 mass% or less, etc.

<Optional epoxy resins other than component (A-1)> In addition to the glycidylamine-type epoxy resin (A-1), the epoxy resin (A) may further contain other optional epoxy resins. Examples of other optional epoxy resins include bixylenol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butyl-catechol epoxy resins, naphthalene epoxy resins, naphthol novolac epoxy resins, Type epoxy resins, anthracene type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing spiro rings, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, naphthyl ether type epoxy resins, trihydroxymethyl type epoxy resins, tetraphenylethane type epoxy resins, etc. The other arbitrary epoxy resins may be used alone or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the other arbitrary epoxy resin. From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more relative to 100% by mass of the non-volatile component of the other arbitrary epoxy resin.

The epoxy resin includes an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resin"). In one embodiment, a liquid epoxy resin is included as another arbitrary epoxy resin. In one embodiment, a solid epoxy resin is included as another arbitrary epoxy resin. A liquid epoxy resin and a solid epoxy resin may also be used in combination.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "EXA-850CRP" manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Chemical Co., Ltd.; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagasechemtex Co., Ltd.; "Celloxide "2021P (CEL2021P)" (epoxy resin with ester skeleton); "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (liquid 1,4-glycidyl cyclohexane type epoxy resin), etc. These can be used alone or in combination of two or more.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

Preferred solid epoxy resins include biphenylol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthyl ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins.

Specific examples of solid epoxy resins include "HP4032H" manufactured by DIC Corporation (naphthalene-based epoxy resin); "HP-4700" and "HP-4710" manufactured by DIC Corporation (naphthalene-based tetrafunctional epoxy resin); "N-690" manufactured by DIC Corporation (cresol novolac-based epoxy resin); "N-695" manufactured by DIC Corporation (cresol novolac-based epoxy resin); "HP-7200" manufactured by DIC Corporation (dicyclopentadiene-based epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-731 1-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; Mitsubishi "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YX4000HK" (xylenol type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; "YX7700" (novolac type epoxy resin containing xylene structure) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Chemical Co., Ltd.; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are combined and used as other arbitrary epoxy resins, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin/solid epoxy resin) is preferably 1 or more, more preferably 10 or more, and particularly preferably 50 or more. By setting the mass ratio of the liquid epoxy resin to the solid epoxy resin in the above range, the desired effect of the present invention can be significantly obtained.

The epoxy equivalent of any other epoxy resin is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., more preferably 80 g/eq. to 2000 g/eq., and even more preferably 110 g/eq. to 1000 g/eq. Within this range, the crosslinking density of the cured resin sheet is sufficient, and an insulating layer with a small surface roughness can be provided. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group.

The weight average molecular weight (Mw) of the other optional epoxy resin is preferably 100 to 5000, more preferably 100 to 3000, and more preferably 100 to 1500 from the viewpoint of significantly obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be obtained as a polystyrene conversion value by measurement by gel permeation chromatography (GPC).

The content of any other epoxy resin is not particularly limited, but when the non-volatile components other than the (D) component in the resin composition are set to 100% by mass, it is preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The lower limit is not particularly limited, and can be, for example, 0% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, etc.

<(B) (Meth) acrylic polymer that is liquid at 25°C> The resin composition of the present invention contains (B) a (meth) acrylic polymer that is liquid at 25°C. Here, the determination of liquid state can be made based on the "Method for Confirming Liquid State" in Annex 2 of the Ministerial Order on the Test and Properties of Hazardous Substances (Ministry of Home Affairs Order No. 1 of 1991). The term "(meth) acrylic polymer" is a concept that includes both acrylic polymer and methacrylic polymer. The terms "(meth) acrylate" and "(meth) acrylamide" are the same. Component (B) can play a role in relieving stress in the cured product of the resin composition.

The so-called (meth)acrylic polymer means a polymer obtained by polymerizing monomer components including (meth)acrylic ester monomers. In addition to (meth)acrylic ester monomers, (meth)acrylic polymers may also include (meth)acrylamide monomers, styrene monomers, monomers containing functional groups, etc. as copolymer components.

Examples of the (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl (meth)acrylate. Aliphatic (meth)acrylates such as tricyclodecyl acrylate; aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate; alkoxy (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-butoxyethyl (meth)acrylate; halogenated (meth)acrylates such as chloroethyl (meth)acrylate and trifluoroethyl (meth)acrylate.

Examples of the (meth)acrylamide monomer include (meth)acrylamide, N-(n-butoxyalkyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide. Examples of the styrene monomer include styrene and α-methylstyrene.

Examples of the monomer containing a functional group include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and a glycidyl group-containing monomer.

Examples of the monomer containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (4-hydroxymethyl)cyclohexylmethyl (meth)acrylate, 2-hydroxyoctyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyoctyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydec ... Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2,2-dimethyl-2-hydroxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and the like.

Examples of the monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, and cinnamic acid. Examples of the monomer containing an amino group include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate. Examples of the monomer containing a glycidyl group include glycidyl (meth)acrylate and allyl glycidyl ether.

Furthermore, the (meth)acrylic polymer may contain an alkoxysilyl group. Examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, and triphenoxysilyl; dialkoxysilyl groups such as dimethoxymethylsilyl and diethoxymethylsilyl; and monoalkoxysilyl groups such as methoxydimethylsilyl and ethoxydimethylsilyl. These alkoxysilyl groups may be present alone or in combination of two or more.

Specific examples of the component (B) include "ARUFON UP-1000", "ARUFON UP-1010", "ARUFON UP-1020", "ARUFON UP-1021", "ARUFON UP-1061", "ARUFON UP-1080", "ARUFON UP-1110", "ARUFON UP-1170", "ARUFON UP-1190", "ARUFON UP-1500", "ARUFON UH-2000", "ARUFON UH-2041", "ARUFON UH-2190", "ARUFON UHE-2012", "ARUFON UC-3510", "ARUFON UG-4010", "ARUFON US-6100", "ARUFON US-6170", etc. These can be used alone or in combination of two or more types.

The glass transition temperature (Tg) of the component (B) is, for example, 20°C or lower, preferably 0°C or lower, further preferably -20°C or lower, further preferably -40°C or lower, and particularly preferably -50°C or lower.

The weight average molecular weight (Mw) of the component (B) is preferably 100 to 20,000, more preferably 200 to 10,000, more preferably 500 to 5,000, and particularly preferably 1,000 to 4,000.

The viscosity of the component (B) at 25°C is preferably 20,000 mPa.s or less, more preferably 10,000 mPa.s or less, and more preferably 5,000 mPa.s or less. The lower limit is not particularly limited, and can be, for example, 100 mPa.s or more, 200 mPa.s or more, or 300 mPa.s or more.

The content of component (B) is not particularly limited, but when the non-volatile components other than component (D) in the resin composition are set to 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 2% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less from the viewpoint of significantly obtaining the desired effect of the present invention.

<(C) Hardener> The resin composition of the present invention includes (C) hardener. (C) Hardener has the function of hardening component (A).

The (C) curing agent is not particularly limited as long as it has the function of curing the epoxy resin, and examples thereof include phenolic curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, benzoxazine curing agents, cyanate curing agents, carbodiimide curing agents, phosphorus curing agents, amine curing agents, imidazole curing agents, guanidine curing agents, and metal curing agents. The curing agent may be used alone or in combination of two or more. The (C) curing agent of the resin composition of the present invention is preferably selected from the group consisting of phenolic curing agents, naphthol curing agents, acid anhydride curing agents, amine curing agents, and imidazole curing agents in order to significantly obtain the desired effect of the present invention. In one embodiment, (C) the hardener preferably includes an active ester hardener.

As the phenolic hardener and the naphthol hardener, from the viewpoint of heat resistance and water resistance, a phenolic hardener having a novolac structure or a naphthol hardener having a novolac structure is preferred. From the viewpoint of adhesion to the adherend, a nitrogen-containing phenolic hardener or a nitrogen-containing naphthol hardener is preferred, and a phenolic hardener containing a triazine skeleton or a naphthol hardener containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, a phenol novolac resin containing a triazine skeleton is preferred. Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemicals, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., and "SN-170", "SN-180", and "SN-190" manufactured by Nippon Steel & Sumitomo Metal Industries, Ltd. "190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" and other products manufactured by DIC Corporation.

Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyrophyllite anhydride, diphenyl Ketone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonate tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-furanyl)-naphthalene[1,2-c]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Polymer type acid anhydrides, etc. Commercially available products of acid anhydride-based hardeners include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

The active ester curing agent is not particularly limited, but generally preferred are compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl 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 hydroxyl 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 the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyrophyllic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, 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, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the so-called "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, preferred are active ester compounds containing dicyclopentadiene diphenol structures, active ester compounds containing naphthalene structures, active ester compounds containing acetyl compounds of phenol novolacs, and active ester compounds containing benzoyl compounds of phenol novolacs. Among them, preferred are active ester compounds containing naphthalene structures and active ester compounds containing dicyclopentadiene diphenol structures. The so-called "dicyclopentadiene diphenol structure" refers to a divalent structural unit consisting of phenylene-pentalene-phenylene.

As commercially available products of active ester-based curing agents, there are "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester compounds containing a naphthalene structure; "DC808" (manufactured by Mitsubishi "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound of a benzoyl compound containing a phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester hardener of an acetyl compound of a phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) as active ester hardeners of benzoyl compounds of phenol novolac, etc.

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industries, Ltd.

Examples of the cyanate curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), Bifunctional cyanate resins such as bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, and prepolymers obtained by triazinization of a part of these cyanate resins, etc. Specific examples of cyanate curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate resins), "BA230", and "BA230S75" (prepolymers in which a part or all of bisphenol A dicyanate is triazinized to form a trimer), etc., manufactured by LONZA Japan Co., Ltd.

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

Examples of the phosphorus-based hardener include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.

Examples of the amine-based curing agent include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and aliphatic amine-based curing agents such as 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene; benzidine, o-tolidine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane (commercially available as "KAYABOND C-100" manufactured by Nippon Kayaku Co., Ltd.), 4,4'-diamino-3,3'-diethyldiphenylmethane (commercially available as "KAYAHARD C-100" manufactured by Nippon Kayaku Co., Ltd.); A-A"), 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane (commercially available as "KAYABOND C-200S" from Nippon Kayaku Co., Ltd.), 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane (commercially available as "KAYABOND C-300S」), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)neopentane, 4,4'-[1,3-phenylenebis(1-methyl-ethylene)]bisaniline ( Aromatic amine-based curing agents such as "bisaniline M" commercially available from Mitsui Chemicals), 4,4'-[1,4-phenylenebis(1-methyl-ethylene)]bisaniline ("bisaniline P" commercially available from Mitsui Chemicals), 2,2-bis[4-(4-aminophenoxy)phenyl]propane ("BAPP" commercially available from Wakayama Seika), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 4,4'-bis(4-aminophenoxy)biphenyl.

Examples of the imidazole curing agent include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazole. , 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1-cyanoethyl-2-undecyl imidazole trimellitate, 1-cyanoethyl-2-phenyl imidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazole-(1')]-ethyl-s-triazine alkylimidazolyl-(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, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, Imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 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 adducts of imidazole compounds with epoxy resins.

As the imidazole-based hardener, a commercially available product can be used, and an example thereof is "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.

Examples of the guanidine-based hardener include 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

Examples of the metal hardener include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, zinc stearate, and the like.

When a hardener is included, the amount ratio of the epoxy resin to the hardener is calculated as [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the hardener], preferably in the range of 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and more preferably 1:0.4 to 1:1.2. Here, the reactive group of the hardener refers to an active hydroxyl group, an active ester group, etc., which varies depending on the type of the hardener. The total number of epoxy groups of the epoxy resin refers to the total value of the values obtained by dividing the mass of the non-volatile components of each epoxy resin by the epoxy equivalent for all epoxy resins; the total number of reactive groups of the hardener refers to the total value of the values obtained by dividing the mass of the non-volatile components of each hardener by the reactive group equivalent for all hardeners. By setting the amount ratio of the epoxy resin to the hardener within the above range, the heat resistance of the obtained hardened material can be further improved.

The content of the component (C) is not particularly limited, but when the non-volatile components other than the component (D) in the resin composition are set to 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, more preferably 60% by mass or less, and particularly preferably 55% by mass or less from the viewpoint of significantly obtaining the desired effect of the present invention.

<(D) Inorganic filler> The resin composition of the present invention contains (D) an inorganic filler.

(D) The material of the inorganic filler is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, alumina, aluminum hydroxide, 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, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Silicon dioxide and aluminum oxide are particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Preferably, the silica is spherical silica. (D) The inorganic filler may be used alone or in combination of two or more.

Commercially available products of (D) inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs; "UFP-30" manufactured by Denka; "Shirufiru NSS-3N", "Shirufiru NSS-4N", and "Shirufiru NSS-5N" manufactured by Tokuyama Co., Ltd.; and "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs.

(D) The average particle size of the inorganic filler is not particularly limited, but from the viewpoint of suppressing the generation of flow marks, it is preferably 40 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. The lower limit of the average particle size of the inorganic filler is not particularly limited, but it is preferably 0.1 μm or more, more preferably 1 μm or more, more preferably 3 μm or more, and more preferably 5 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction-scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared based on the volume by using a laser diffraction scattering particle size distribution measuring device, and the median particle size can be used as the average particle size for measurement. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them by ultrasound for 10 minutes. For the measurement sample, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source is set to blue and red. The volume-based particle size distribution of the inorganic filler is measured by a flow cell method, and the average particle size as the median particle size is calculated from the obtained particle size distribution. Examples of laser diffraction particle size distribution measuring devices include "LA-960" manufactured by Horiba, Ltd.

From the viewpoint of improving moisture resistance and dispersibility, the (D) inorganic filler is preferably treated with one or more surface treatment agents selected from the group consisting of aminosilane coupling agents, epoxysilane coupling agents, butylsilane coupling agents, alkoxysilane compounds, organic silazane compounds, and titanium ester coupling agents. Examples of commercially available surface treatment agents include "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-hydroxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "SZ-3 1" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM503" (3-methacryloyloxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM5783", etc.

The degree of surface treatment by the surface treatment agent is preferably set within a specified range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% by mass to 5% by mass of the surface treatment agent, preferably 0.2% by mass to 3% by mass, and preferably 0.3% by mass to 2% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated based on the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ ^m2 or more, more preferably 0.1 mg/ ^m2 or more, and more preferably 0.2 mg/ ^m2 or more. On the other hand, from the perspective of preventing the increase in the melt viscosity of the resin varnish or the melt viscosity in the form of a sheet, it is preferably 1 mg/ ^m2 or less, more preferably 0.8 mg/ ^m2 or less, and more preferably 0.5 mg/ ^m2 or less.

(D) The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

(D) The specific surface area of the inorganic filler is preferably 0.01 m ² /g or more, more preferably 0.1 m ² /g or more, and particularly preferably 0.2 m ² /g or more, from the viewpoint of further enhancing the effect of the present invention. The upper limit is not particularly limited, but is preferably 50 m ² /g or less, more 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 obtained by adsorbing nitrogen on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method.

(D) The content of the inorganic filler is not particularly limited, but when all non-volatile components in the resin composition are set to 100% by mass, from the perspective of use for a specific purpose, it is preferably 20% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit is not particularly limited, but can be, for example, 98% by mass or less, 95% by mass or less, 92% by mass or less, 90% by mass or less, etc.

<(E) Organic solvent> The resin composition of the present invention may further contain (E) an organic solvent as an arbitrary volatile component.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, solvent acetate, propylene glycol monomethyl ether acetate, carbitol acetate, diethylene glycol ethyl ether acetate, and γ-butyrolactone; carbitol solvents such as solvent and butyl carbitol; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone; alcohol solvents such as methanol, ethanol, and 2-methoxypropanol; hydrocarbon solvents such as cyclohexane and methylcyclohexane, etc. The organic solvent may be used alone or in combination of two or more at any ratio.

In one embodiment, the resin composition of the present invention preferably does not contain an organic solvent.

<(F) Other additives> In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Such additives include, for example, organic fillers, thickeners, defoamers, leveling agents, adhesion agents, polymerization initiators, flame retardants, etc. Such additives may be used alone or in combination of two or more. The respective contents may be appropriately set by a person having ordinary knowledge in the relevant technical field.

<Manufacturing method of resin composition> In one embodiment, the resin composition of the present invention can be manufactured by a method comprising the following steps, for example, in a reaction container, (A) epoxy resin, (B) (meth) acrylic polymer that is liquid at 25°C, (C) hardener, (D) inorganic filler, (E) organic solvent as required, and (F) other additives as required are added in any order and/or partially or all at the same time, and mixed to obtain the resin composition.

In the above steps, the temperature of the process of adding each component can be appropriately set, and heating and/or cooling can be performed temporarily or throughout the process of adding each component. Stirring or shaking can be performed during the process of adding each component. In addition, after the above steps, it is preferred to further include a step of stirring the resin composition using a stirring device such as a stirrer to make it uniformly dispersed.

<Characteristics of the resin composition> Since the resin composition of the present invention contains (A) epoxy resin, (B) (meth) acrylic polymer that is liquid at 25°C, (C) hardener and (D) inorganic filler, and component (A) includes (A-1) glycidylamine type epoxy resin, the warping of the cured product can be suppressed, and the cured film after environmental testing can be obtained to have excellent adhesion to the load in the vertical direction. In addition, in one embodiment, the resin composition of the present invention can suppress the generation of flow marks.

In one embodiment, a cured layer of the resin composition of the present invention (300 μm thick; heat cured at 180° C. for 90 minutes) is bonded to a substrate comprising a 12-inch silicon wafer, and the warp at 25° C. measured in accordance with the JEITA EDX-7311-24 standard of the Electronics and Information Technology Industry Association is preferably less than 5 mm, more preferably less than 4 mm, more preferably less than 3 mm, and particularly preferably less than 2 mm.

In one embodiment, the hardened layer (thickness 50 μm; heat hardening at 180°C for 90 minutes) of the resin composition of the present invention after high temperature and high humidity environment test (130°C 85% RH 96 hours) has an adhesion strength to a silicon wafer of preferably 300 Kgf/ ^cm2 or more, more preferably 400 Kgf/ ^cm2 or more, more preferably 450 Kgf/ ^cm2 or more, and particularly preferably 500 Kgf/cm2 or more when subjected to a vertical tensile test at ^0.1 Kg/sec.

<Use of resin composition> The cured resin composition of the present invention is useful for the sealing layer and insulating layer of a semiconductor due to the above-mentioned advantages. Therefore, the resin composition can be used as a resin composition for semiconductor sealing or insulating layer.

For example, the resin composition of the present invention can be used as a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for insulating layer of a semiconductor chip package) and a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (resin composition for insulating layer of a circuit board).

Furthermore, for example, the resin composition of the present invention can be suitably used as a resin composition for sealing a semiconductor chip in a semiconductor chip package (resin composition for semiconductor chip sealing).

Semiconductor chip packages to which a sealing layer or an insulating layer formed by a cured product of the resin composition of the present invention can be applied include, for example, FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP.

Furthermore, the resin composition of the present invention can be used as an underfill material, and can also be used as a MUF (Molding Under Filling) material used after connecting a semiconductor chip to a substrate.

Furthermore, the resin composition of the present invention can be used in a wide range of resin compositions such as resin sheets, prepregs and other sheet-like laminate materials, liquid materials such as resin inks for solder resists, etc., grain bonding materials, hole filling resins, and component embedding resins.

<Resin sheet> The resin sheet of the present invention has a support and a resin composition layer disposed on the support. The resin composition layer is a layer including the resin composition of the present invention, and is usually formed of a resin composition.

The thickness of the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less, from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 100 μm or more.

Furthermore, the thickness of the cured product obtained by curing the resin composition layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 100 μm or more.

Examples of the support include films made of plastic materials, metal foils, and release papers, preferably films made of plastic materials or metal foils.

When a film made of a plastic material is used as the support, the plastic material may include polyesters such as polyethylene terephthalate (hereinafter referred to as "PET") and polyethylene naphthalate (hereinafter referred to as "PEN"), polycarbonate (hereinafter referred to as "PC"), acrylic polymers such as polymethyl methacrylate (hereinafter referred to as "PMMA"), cyclic polyolefin, triacetyl cellulose (hereinafter referred to as "TAC"), polyether sulfide (hereinafter referred to as "PES"), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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 preferred. The copper foil may be a foil made of a single metal containing copper or a foil made of an alloy containing copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

The surface of the support body that is bonded to the resin composition layer may be subjected to polishing, corona treatment, anti-static treatment, and the like.

In addition, as the support body, a support body with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used for the release layer of the support body with a release layer, for example, at least one release agent selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins can be cited. As commercially available release agents, for example, alkyd resin release agents such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation can be cited. Examples of the support body with a release layer include "Lumirror T60" manufactured by Toray Industries, Inc., "PUREX" manufactured by Teijin Ltd., and "Unipeel" manufactured by Unitika Co., Ltd.

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

The resin sheet can be manufactured by coating the resin composition on a support using a coating device such as a die coater. Alternatively, the resin composition can be dissolved in an organic solvent to prepare a resin varnish as required, and the resin varnish can be coated to manufacture the resin sheet. The coating property can be improved by adjusting the viscosity using a solvent. When using a resin varnish, the resin varnish is usually dried after coating to form a resin composition layer.

Drying can be carried out by known methods such as heating and hot air blowing. 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. It varies depending on the boiling point of the organic solvent in the resin varnish. For example, if a resin varnish containing 30% to 60% by mass of an organic solvent is used, the resin composition layer can be formed by drying it at 50°C to 150°C for 3 minutes to 10 minutes.

As required, the resin sheet may include any layer other than the support and the resin component layer. For example, in the resin sheet, the surface that is not joined to the support of the resin component layer (i.e., the surface on the opposite side of the support) may be provided with a protective film in conjunction with the support. The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent impurities and the like from adhering to or scratching the surface of the resin component 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 rolled into a tube for storage.

When manufacturing semiconductor chip packages, resin sheets can be used to form insulating layers (resin sheets for insulating semiconductor chip packages). For example, resin sheets can be used to form insulating layers of circuit boards (resin sheets for insulating layers of circuit boards). Examples of packages using such substrates include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

Furthermore, the resin sheet can be used to seal a semiconductor chip (resin sheet for semiconductor chip sealing). Examples of semiconductor chip packages that can be used include Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, and Fan-in type PLP.

In addition, the resin sheet can also be used as a MUF material used after the semiconductor chip is connected to the substrate.

Furthermore, the resin sheet can be used in a wide range of other applications requiring high insulation reliability. For example, the resin sheet can be suitably used to form an insulation layer of a circuit board such as a printed wiring board.

<Circuit board> The circuit board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. The circuit board can be manufactured by a manufacturing method including, for example, the following steps (1) and (2). (1) A step of forming a resin composition layer on a substrate. (2) A step of thermally curing the resin composition layer to form an insulating layer.

In step (1), a substrate is prepared. Examples of the substrate include glass epoxy substrates, metal substrates (stainless steel or cold-rolled steel (SPCC) substrates, etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Furthermore, the substrate may have a metal layer such as copper foil on the surface as a part of the substrate. For example, a substrate having a first metal layer and a second metal layer that can be peeled off on both surfaces may be used. When such a substrate is used, a conductive layer serving as a wiring layer is usually formed on the surface of the second metal layer that is opposite to the first metal layer, and the wiring layer can function as a circuit wiring. As a substrate having such a metal layer, for example, there is an ultra-thin copper foil "Micro Thin" with a carrier copper foil manufactured by Mitsui Mining & Co., Ltd.

Furthermore, a conductive layer may be formed on one or both surfaces of the substrate. In the following description, the substrate and the conductive layer formed on the surface of the substrate will be appropriately referred to as a "substrate with a wiring layer". As the conductive material contained in the conductive layer, there can be cited a material containing one or more metals selected from the group consisting of, for example, gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. As the conductive material, a single metal or an alloy can be used. As the alloy, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper.titanium alloy) can be cited. Among them, from the viewpoint of versatility, cost, and ease of patterning of the conductor layer formation, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal, and nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy as an alloy are preferred. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal, and nickel-chromium alloy are more preferred; copper as a single metal is particularly preferred.

In order to make the conductor layer function as a wiring layer, for example, the conductor layer can be patterned. At this time, the line width (circuit width)/spacing (width between circuits) ratio of the conductor layer is not particularly limited, and is preferably 20/20μm or less (i.e., the spacing is 40μm or less), more preferably 10/10μm or less, more preferably 5/5μm or less, more preferably 1/1μm or less, and particularly preferably 0.5/0.5μm or more. The overall spacing of the conductor layer does not need to be the same. The minimum spacing of the conductor layer can be set to, for example, 40μm or less, 36μm or less, or 30μm or less.

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

The conductive layer can be formed by a method including, for example, the following steps: a step of laminating a dry film (photosensitive resist film) on a substrate; a step of exposing and developing the dry film under specified conditions using a photomask to form a pattern to obtain a patterned dry film; a step of using the developed patterned dry film as a coating mask and forming a conductive layer by a coating method such as an electrolytic coating method; and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film containing a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. The lamination conditions between the substrate and the dry film can be the same as the lamination conditions between the substrate and the resin sheet described below. The stripping of the dry film can be carried out using an alkaline stripping solution such as a sodium hydroxide solution.

After the substrate is prepared, a resin composition layer is formed on the substrate. If a conductor layer is formed on the surface of the substrate, the resin composition layer is preferably formed such that the conductor layer is buried in the resin composition layer.

The formation of the resin composition layer can be performed by laminating a resin sheet and a substrate, for example. The lamination can be performed by, for example, heating and pressing the resin sheet onto the substrate from the side of the support so that the resin composition layer is attached to the substrate. As a member for heating and pressing the resin sheet onto the substrate (hereinafter sometimes referred to as a "heating and pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller, etc.) can be cited. However, it is preferred that the heating and pressing member is not directly pressed onto the resin sheet, but the resin sheet is pressed through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface irregularities of the substrate.

The lamination of the substrate and the resin sheet can be performed by, for example, a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa. The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure conditions with a pressure of less than 13hPa.

After lamination, the laminated resin sheet can be smoothed by pressing the heated pressing member from the support body side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be set to the same conditions as the heated pressing conditions for the lamination. In addition, the lamination and smoothing treatment can be performed continuously using a vacuum laminating machine.

The resin composition layer can be formed by, for example, compression molding. The molding conditions can be the same as those of the resin composition layer forming method in the step of forming the sealing layer of the semiconductor chip package described later.

After forming the resin composition layer on the substrate, the resin composition layer is heat-cured to form an insulating layer. Although the heat-curing conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is generally in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, and more preferably in the range of 170°C to 200°C), and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, and more preferably 15 minutes to 90 minutes).

Before the resin composition layer is heat-cured, the resin composition layer may be pre-heated at a temperature lower than the curing temperature. For example, before the resin composition layer is heat-cured, the resin composition layer may be pre-heated at a temperature of 50°C to 120°C (preferably 60°C to 110°C, and more preferably 70°C to 100°C) for 5 minutes or more (preferably 5 minutes to 150 minutes, and more preferably 15 minutes to 120 minutes).

By performing the above operation, a circuit substrate having an insulating layer can be manufactured. In addition, the method for manufacturing a circuit substrate may further include an arbitrary step. For example, when a resin sheet is used to manufacture a circuit substrate, the method for manufacturing a circuit substrate may include a step of peeling off a support body of the resin sheet. The support body may be peeled off before the resin component layer is thermally cured, or may be peeled off after the resin component layer is thermally cured.

The manufacturing method of the circuit substrate may include, for example, the following steps: after forming the insulating layer, grinding the surface of the insulating layer. The grinding method is not particularly limited. For example, a surface grinding disc may be used to grind the surface of the insulating layer.

The manufacturing method of the circuit substrate may include, for example, the step (3) of connecting the conductor layers between layers, that is, the step of opening holes on the insulating layer. In this way, holes such as through holes and through holes can be formed on the insulating layer. As a method for forming through holes, for example, laser irradiation, etching, mechanical drilling, etc. can be cited. The size or shape of the through hole can be appropriately determined according to the design of the circuit substrate. In addition, step (3) can be performed by grinding or grinding the insulating layer to connect the layers between layers.

After the through hole is formed, it is preferred to perform a step of removing the glue residue in the through hole. This step is called a desmearing step. For example, when the conductive layer is formed on the insulating layer by a plating step, a wet desmearing treatment can be performed on the through hole. Also, when the conductive layer is formed on the insulating layer by a sputtering step, a dry desmearing step such as a plasma treatment step can be performed. Furthermore, the insulating layer can also be roughened by the desmearing step.

Furthermore, before forming the conductive layer on the insulating layer, the insulating layer may be subjected to a roughening treatment. According to the roughening treatment, the surface of the insulating layer including the through hole is usually roughened. The roughening treatment may be either a dry roughening treatment or a wet roughening treatment. Examples of dry roughening treatments include plasma treatment and the like. Furthermore, examples of wet roughening treatments include a method of sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.

After forming the through-holes, a conductive layer can be formed on the insulating layer. By forming a conductive layer at the location where the through-holes are formed, the newly formed conductive layer can be electrically connected to the conductive layer on the surface of the substrate to achieve inter-layer connection. The conductive layer can be formed by, for example, plating, sputtering, evaporation, etc., among which plating is preferred. In a suitable embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method and a full-additive method to form a conductive layer having a desired wiring pattern. Furthermore, if the support in the resin sheet is a metal foil, a conductive layer having a desired wiring pattern can be formed by a subtractive method. The material of the formed conductive layer may be a single metal or an alloy. Furthermore, the conductive layer may have a single layer structure or a multi-layer structure including two or more layers of different types of materials.

Here, an example of an implementation form of forming a conductive layer on an insulating layer is described in detail. A coating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed coating seed layer in a manner corresponding to the desired wiring pattern to expose a portion of the coating seed layer. An electrolytic coating layer is formed on the exposed coating seed layer by electrolytic plating, and the mask pattern is removed. Thereafter, the unnecessary coating seed layer is removed by etching or the like, and a conductive layer having the desired wiring pattern can be formed. In addition, when forming the conductive layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

The method for manufacturing a circuit substrate may include a step (4) of removing a substrate. By removing the substrate, a circuit substrate having an insulating layer and a conductive layer (which is embedded in the insulating layer) can be obtained. The step (4) can be performed, for example, when a substrate having a metal layer that can be peeled off is used.

<Semiconductor chip package> The semiconductor chip package related to the first embodiment of the present invention comprises the above-mentioned circuit substrate and a semiconductor chip mounted on the circuit substrate. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit substrate.

The bonding conditions between the circuit board and the semiconductor chip may be any conditions that allow the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board to be conductively connected. For example, the conditions used in flip chip mounting of the semiconductor chip may be used. 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 can be cited a method of pressing a semiconductor chip onto a circuit board. As pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, and more preferably in the range of 140°C to 180°C), and the pressing time is usually in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

As another example of the bonding method, there is a method of bonding a semiconductor chip to a circuit board by reflowing. The reflow condition can be set in the range of 120°C to 300°C.

After the semiconductor chip is bonded to the circuit substrate, the semiconductor chip can be filled with a molded bottom filler. As the molded bottom filler, the above-mentioned resin composition can be used, and the above-mentioned resin sheet can also be used.

The semiconductor chip package according to the second embodiment of the present invention comprises a semiconductor chip and a hardened resin composition for sealing the semiconductor chip. In such a semiconductor chip package, generally speaking, the hardened resin composition functions as a sealing layer. As a semiconductor chip package according to the second embodiment, a Fan-out type WLP can be cited.

Such a method for manufacturing a semiconductor chip package includes the following steps: (A) laminating a temporary fixing film on a substrate; (B) temporarily fixing a semiconductor chip on the temporary fixing film; (C) forming a sealing layer on the semiconductor chip; (D) peeling the substrate and the temporary fixing film from the semiconductor chip; (E) forming a redistribution layer as an insulating layer on the surface of the semiconductor chip where the substrate and the temporary fixing film are peeled; (F) forming a redistribution layer as a conductive layer on the redistribution layer; and (G) forming a solder resist layer on the redistribution layer. Furthermore, the aforementioned method for manufacturing a semiconductor chip package may also include the step of (H) cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into individual pieces.

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

Examples of the substrate include silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheets (SPCC), substrates such as FR-4 substrates in which glass fibers are infiltrated with epoxy resins and then heat-cured, and substrates such as BT resins containing dimaleimide triazine resins.

The temporary fixing film may be any material that can be peeled off from the semiconductor chip and temporarily fix the semiconductor chip. Examples of commercially available products include "REVALPHA" manufactured by Nitto Denko Corporation.

(Step (B)) Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonding machine or a die bonder. The configuration layout and number of semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor chip package, etc. For example, the semiconductor chips can be arranged in a matrix of multiple rows and multiple columns for temporary fixing.

(Step (C)) Step (C) is a step of forming a sealing layer on a semiconductor chip. The sealing layer is formed by hardening the resin composition described above. Generally, the sealing layer is formed by a method comprising the steps of forming a resin composition layer on a semiconductor chip and thermally hardening the resin composition layer to form the sealing layer.

Taking advantage of the excellent compression molding properties of the resin composition, it is preferred to form the resin composition layer by compression molding. Generally speaking, the compression molding method is to place the semiconductor chip and the resin composition in a mold, apply pressure to the resin composition in the mold and apply heat as needed to form the resin composition layer covering the semiconductor chip.

The specific operation of the compression molding method can be as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. In addition, a resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition is fixed to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper mold and the lower mold are combined, and heat and pressure are applied to the resin composition to perform compression molding.

The specific operation of the compression molding method can also be performed in the following manner, for example. An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed in the lower mold. A semiconductor chip is fixed to the upper mold together with a substrate and a temporary fixing film. Thereafter, the upper mold and the lower mold are combined in such a manner that the resin composition placed in the lower mold is in contact with the semiconductor chip fixed in the upper mold, and heat and pressure are applied to perform compression molding.

The molding conditions vary depending on the composition of the resin composition, and appropriate conditions that can achieve good sealing can be adopted. For example, the mold temperature during molding is preferably a temperature that can bring into play the excellent compression molding properties of the resin composition, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. In addition, the pressure applied during molding is preferably 1MPa or higher, more preferably 3MPa or higher, particularly preferably 5MPa or higher, preferably 50MPa or lower, more preferably 30MPa or lower, and particularly preferably 20MPa or lower. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, particularly preferably 20 minutes or less. Generally speaking, the mold can be removed after the resin composition layer is formed. The mold can be removed before or after the resin composition layer is thermally cured.

The resin composition layer can be formed by laminating the resin sheet and the semiconductor chip. For example, the resin composition layer of the resin sheet and the semiconductor chip can be formed on the semiconductor chip by heating and pressing. The lamination of the resin sheet and the semiconductor chip can generally be performed in the same manner as the lamination of the resin sheet and the substrate in the manufacturing method of the circuit board, but the semiconductor chip is used instead of the substrate.

After forming a resin composition layer on a semiconductor chip, the resin composition layer is heat-cured to obtain a sealing layer covering the semiconductor chip. Accordingly, the semiconductor chip can be sealed by the cured resin composition. The heat-curing conditions of the resin composition layer can be the same as the heat-curing conditions of the resin composition layer in the method for manufacturing a circuit board. Furthermore, before heat-curing the resin composition layer, a preliminary heat treatment can be performed by heating the resin composition layer at a temperature lower than the curing temperature. The treatment conditions of the preliminary heat treatment can be the same as the treatment conditions of the preliminary heat treatment in the method for manufacturing a circuit board.

(Step (D)) Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. The peeling method is preferably a method suitable for the material of the temporary fixing film. As a peeling method, there can be exemplified a method of peeling the temporary fixing film by heating, foaming or expanding the temporary fixing film. Also, as a peeling method, there can be exemplified a method of irradiating the temporary fixing film with ultraviolet light through the substrate to reduce the adhesion of the temporary fixing film and then peeling it.

In the method of peeling off the temporary fixing film by heating, foaming or expanding it, the heating condition is usually 100℃~250℃ for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of peeling off after irradiating ultraviolet rays to reduce the adhesive force of the temporary fixing film, the irradiation amount of ultraviolet rays is usually 10mJ/ ^cm2 ~1000mJ/ ^cm2 .

(Step (E)) Step (E) is a step of forming a redistribution layer as an insulating layer on the substrate of the semiconductor chip and the surface where the temporary fixing film is peeled off.

The material of the redistribution forming layer can be any material having insulation properties. Among them, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing the semiconductor chip package. In addition, as the thermosetting resin, the resin composition of the present invention can be used.

After the redistribution formation layer is formed, a through hole may be formed on the redistribution formation layer in order to connect the semiconductor chip to the redistribution formation layer.

If the material of the redistribution forming layer is a photosensitive resin, generally speaking, the method for forming the through hole is to irradiate the surface of the redistribution forming layer with active energy rays through a mask pattern to photoharden the irradiated portion of the redistribution forming layer. Examples of active energy rays include ultraviolet rays, visible rays, electron rays, X-rays, etc., with ultraviolet rays being particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. Examples of the exposure method include: a contact exposure method in which a mask pattern is adhered to the redistribution forming layer and then exposed; and a non-contact exposure method in which a mask pattern is not adhered to the redistribution forming layer and then exposed using parallel light.

After the redistribution formation layer is photocured, the redistribution formation layer is developed and the unexposed portion is removed to form a through hole. The development may be either wet development or dry development. Examples of the development method include immersion, mixing, spraying, brushing, and scraping. From the perspective of analytical performance, the mixing method is suitable.

When the material of the redistribution forming layer is a thermosetting resin, the method of forming the through hole may be, for example, laser irradiation, etching, mechanical drilling, etc. Among them, laser irradiation is preferred. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide gas laser, a UV-YAG laser, or an excimer laser.

The shape of the through hole is not particularly limited, and is generally circular (slightly circular). The top end diameter of the through hole is preferably less than 50 μm, more preferably less than 30 μm, more preferably less than 20 μm, more preferably more than 3 μm, more preferably more than 10 μm, and more preferably more than 15 μm. Here, the so-called top end diameter of the through hole refers to the diameter of the opening of the through hole on the surface of the redistribution formation layer.

(Step (F)) Step (F) is a step of forming a redistribution layer as a conductive layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer can be the same as the method of forming a conductive layer on the insulating layer in the manufacturing method of the circuit board. In addition, the redistribution layer and the redistribution formation layer can be alternately stacked (layer build-up) by repeating step (E) and step (F).

(Step (G)) Step (G) is a step of forming a solder resist layer on the redistribution layer. The material of the solder resist layer can be any material having insulation properties. Among them, photosensitive resins and thermosetting resins are preferred from the perspective of ease of manufacturing the semiconductor chip package. In addition, as the thermosetting resin, the resin composition of the present invention can be used.

In step (G), bump processing can be performed to form bumps as needed. The bump processing can be performed by using solder balls, solder plating, etc. In addition, the formation of through holes in the bump processing can be performed in the same way as in step (E).

(Step (H)) In addition to steps (A) to (G), the method for manufacturing a semiconductor chip package may include step (H). Step (H) is a step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into individual pieces. The method for cutting a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

<Semiconductor device> A semiconductor device is a semiconductor chip package. Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, smart phones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and transportation vehicles (such as motorcycles, cars, trains, ships, and airplanes). [Example]

The present invention is specifically described below by way of examples. The present invention is not limited to the examples. In addition, the "parts" and "%" used below to indicate quantities have the meanings of "parts by mass" and "% by mass" respectively unless otherwise specified.

<Example 1> Two parts of glycidylamine epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115 g/eq.) and two parts of glycidylamine epoxy resin (Mitsubishi A resin composition was prepared by uniformly dispersing 3 parts of "630LSD" manufactured by Chemical Co., Ltd., epoxy equivalent 95 g/eq.), 1 part of liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd., viscosity (25°C) 500 mPa.s, Mw 2,000, Tg -80°C), 6 parts of bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent 170-175 g/eq.), 6 parts of acid anhydride hardener ("HNA-100" manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 179 g/eq.), 83 parts of silica A, and 0.1 parts of imidazole hardener ("2E4MZ" manufactured by Shikoku Chemical Co., Ltd., 2-ethyl-4-methylimidazole) using a stirrer.

<Example 2> Except for using 1 part of liquid acrylic polymer ("UG-4010" manufactured by Toagosei Co., Ltd., viscosity (25℃) 3,700mPa.s, Mw 2,900, Tg-57℃) instead of 1 part of liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd.), the resin composition is prepared in the same manner as in Example 1.

<Example 3> Except for using 1 part of liquid acrylic polymer ("US-6100" manufactured by Toagosei Co., Ltd., viscosity (25°C) 2,300 mPa.s, Mw 2,500, Tg -58°C) instead of 1 part of liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd.), the resin composition is prepared in the same manner as in Example 1.

<Example 4> 1 part of glycerylamine epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115 g/eq.), 1 part of glycerylamine epoxy resin (Mitsubishi A resin composition was prepared by uniformly dispersing 10 parts of "630LSD" manufactured by Chemical Co., Ltd., epoxy equivalent 95 g/eq.), 1 part of liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd., viscosity (25°C) 500 mPa.s, Mw 2,000, Tg -80°C), 1 part of bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent 170 to 175 g/eq.), 1 part of phenolic hardener ("MEH-8000H" manufactured by Meiwa Chemical Co., Ltd.), 83 parts of silica A, and 0.4 parts of imidazole hardener ("2E4MZ" manufactured by Shikoku Chemical Co., Ltd., 2-ethyl-4-methylimidazole) using a stirrer to prepare a resin composition.

<Example 5> Except for using 1 part of amine hardener ("KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd.) to replace 1 part of phenol hardener ("MEH-8000H" manufactured by Meiwa Chemicals Co., Ltd.), the resin composition is prepared in the same manner as in Example 4.

<Example 6> Except for using 95 parts of aluminum oxide A instead of 83 parts of silicon dioxide A, the resin composition is prepared in the same manner as in Example 1.

<Example 7> The resin composition was prepared in the same manner as in Example 1 except that the amount of the glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 95 g/eq.) was increased to 3.5 parts and the amount of the liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd.) was reduced to 0.5 parts.

<Example 8> 4 parts of glycerylamine epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115 g/eq.) and 4 parts of glycerylamine epoxy resin (Mitsubishi A resin composition was prepared by uniformly dispersing 9 parts of "630LSD" manufactured by Chemical Co., Ltd., epoxy equivalent 95 g/eq.), 1 part of liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd., viscosity (25°C) 500 mPa.s, Mw 2,000, Tg -80°C), 4 parts of acid anhydride hardener ("HNA-100" manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 179 g/eq.), 83 parts of silica A, and 0.1 part of imidazole hardener ("2E4MZ" manufactured by Shikoku Chemical Co., Ltd., 2-ethyl-4-methylimidazole) using a stirrer.

<Example 9> 1 part of glycerylamine epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115 g/eq.), 1 part of glycerylamine epoxy resin (Mitsubishi A resin composition was prepared by uniformly dispersing 1 part of "630LSD" manufactured by Chemical Co., Ltd., epoxy equivalent 95 g/eq.), 1 part of liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd., viscosity (25°C) 500 mPa.s, Mw 2,000, Tg -80°C), 9 parts of bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent 170-175 g/eq.), 6 parts of acid anhydride hardener ("HNA-100" manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 179 g/eq.), 83 parts of silica A, and 0.1 parts of imidazole hardener ("2E4MZ" manufactured by Shikoku Chemical Co., Ltd., 2-ethyl-4-methylimidazole) using a stirrer to prepare a resin composition.

<Example 10> The resin composition was prepared in the same manner as in Example 1, except that the amount of bisphenol A epoxy resin ("EXA-850CRP" manufactured by DIC Corporation, epoxy equivalent 170-175 g/eq.) was reduced to 2 parts and the amount of liquid acrylic polymer ("UP-1020" manufactured by Toagosei Corporation) was increased to 5 parts.

<Comparative Example 1> The resin composition was prepared in the same manner as in Example 1 except that the acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd.) was not used.

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

<Test Example 1: Evaluation of Warp> On a 12-inch silicon wafer, the resin composition prepared in the embodiment and the comparative example was compression molded using a compression molding device (mold temperature: 130°C, pressure: 6MPa, curing time: 10 minutes) to form a resin composition layer with a thickness of 300μm. Thereafter, the resin composition layer was thermally cured by heating at 180°C for 90 minutes. Thus, a sample substrate including a silicon wafer and a cured layer of the resin composition was obtained. The warp of the aforementioned sample substrate at 25°C was measured using a shadow overlay measuring device ("Thermoire AXP" manufactured by Akorometrix). The measurement is performed in accordance with JEITA EDX-7311-24 stipulated by the Electronics and Information Technology Industries Association. Specifically, all data on the substrate surface of the measurement area is used to calculate a hypothetical plane as a reference plane by the least square method, and the difference between the minimum and maximum values in the vertical direction from the reference plane is obtained as the warp amount. If the warp amount is less than 2mm, it is evaluated as "○"; if it is more than 2mm and less than 3mm, it is evaluated as "△"; if it is more than 3mm, it is evaluated as "×".

<Test Example 2: Evaluation of Appearance> Observe the appearance of the resin layer of the sample substrate produced in Test Example 1. If the area of the flow mark in the entire surface of the resin layer is less than 20%, it is evaluated as "0"; if it exceeds 20%, it is evaluated as "△".

<Test Example 3: Adhesion Evaluation after High Temperature and High Humidity Environment Test (HAST)> Using the sample substrate prepared in Test Example 1, a high temperature and high humidity environment test (HAST) was performed at 130°C and 85% RH for 96 hours. The hardened material after HAST was polished using #180 sandpaper until the resin layer became 50μm thick. The polished sample was cut into a 1cm square specimen. For the resin layer, a φ2.7mm stud pin with adhesive was placed upright and perpendicular to the resin layer and heated at 150°C for 60 minutes to produce a specimen in which the stud pin and the resin layer were bonded. The obtained specimen with stud pin was subjected to vertical tensile test using ROMULUS vertical tensile tester manufactured by QUAD GROUP at a test rate of 0.1 kg/sec. Five specimens were measured and the average value was calculated. If the adhesion strength exceeded 500 kgf/ ^cm2 , it was evaluated as "0", and if it was less than 500 kgf/ ^cm2 , it was evaluated as "×".

The non-volatile components of the resin compositions of Examples and Comparative Examples and their usage amounts, as well as the evaluation results of the test examples are shown in Table 1 below.

The above results show that when (A-1) glycidylamine epoxy resin and (B) (meth)acrylic polymer that is liquid at 25°C are used, the warping of the cured product can be suppressed and the cured film after environmental testing can achieve excellent adhesion to a load in the vertical direction.

Claims (16)

A resin composition comprising (A) an epoxy resin, (B) a (meth) acrylic polymer that is liquid at 25°C, (C) a hardener, and (D) an inorganic filler, wherein the component (A) comprises a glycidylamine-type epoxy resin, and when the non-volatile components other than the component (D) in the resin composition are taken as 100% by mass, the content of the component (A-1) is 10% by mass to 90% by mass, the content of the component (B) is 0.01% by mass to 40% by mass, and the content of the component (C) is 0.1% by mass to 70% by mass. The resin composition of claim 1, wherein the component (A-1) is a difunctional or trifunctional glycidylamine type epoxy resin. The resin composition of claim 1, wherein the content of the component (A-1) is 20% by mass or more and 80% by mass or less when the non-volatile components other than the component (D) in the resin composition are taken as 100% by mass. The resin composition of claim 1, wherein the content of component (B) is 0.5% by mass or more and 20% by mass or less when the non-volatile components other than component (D) in the resin composition are taken as 100% by mass. The resin composition of claim 1, wherein the component (C) is a hardener selected from the group consisting of phenol hardeners, naphthol hardeners, acid anhydride hardeners, amine hardeners and imidazole hardeners. The resin composition of claim 1, wherein the content of component (D) is 70% by mass or more when all non-volatile components in the resin composition are taken as 100% by mass. The resin composition of claim 1 is used to form an insulating layer of a semiconductor chip package. The resin composition of claim 1 is used to form an insulating layer of a circuit substrate. The resin composition of claim 1 is used to seal the semiconductor chip of the semiconductor chip package. A cured product of a resin composition as described in any one of claims 1 to 9. A resin sheet having a support and a resin composition layer disposed on the support, wherein the resin composition layer comprises a resin composition as described in any one of claims 1 to 9. A circuit substrate comprising an insulating layer formed by a cured product of a resin composition as described in any one of claims 1 to 9. A semiconductor chip package, comprising a circuit substrate as claimed in claim 12 and a semiconductor chip mounted on the circuit substrate. A semiconductor device having a semiconductor chip package as claimed in claim 13. A semiconductor chip package, comprising a semiconductor chip and a hardened resin composition as described in any one of claims 1 to 9 for sealing the semiconductor chip. A semiconductor device having a semiconductor chip package as claimed in claim 15.