TW202041594A - Resin composition including glycidylamine epoxy resin - Google Patents

Abstract

The subject of the present invention is to provide a resin composition that can suppress a warpage of a cured product and has an excellent seal effect of a load in a vertical direction of a cured film after performing an environmental test. The resin composition includes (A) an epoxy resin, (B) a (meth)acrylic polymer which is in liquid state at 25 DEG C, (C) a hardener, and (D) an inorganic filler. Component (A) further includes (A-1) a glycidylamine epoxy resin. The resin composition may form an insulation layer of a package of a semiconductor chip or an insulation layer of a circuit substrate. The resin composition may be used for sealing a package of a semiconductor chip. The resin composition, excluding component (D), may include about 20 percent to 80 percent in mass of component (A1) and about 0.5 percent to 20 percent in mass of component (B).

Description

Resin composition

The present invention relates to: a resin composition containing an epoxy resin and a curing agent; a cured product of the above resin composition; a resin sheet containing the above resin composition; a circuit board containing the above cured product; a semiconductor chip package containing the above cured product Body; and a semiconductor device provided with the above-mentioned semiconductor chip package.

In recent years, due to the increasing demand for small high-performance electronic devices such as smart phones and tablet devices, along with this, the insulating materials for semiconductor chip packages used in these small electronic devices are also required to be more functional . Such an insulating layer is known to be formed by curing a resin composition (see, for example, Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2017-008312 A

[The problem to be solved by the invention]

Especially in recent years, a smaller semiconductor chip package is required, so the thickness of the insulating layer or sealing material used in the semiconductor chip package, and the silicon chip itself is also required to be thinner. Therefore, the development of an insulating layer that can suppress warpage even if the thickness is thinner is expected.

However, due to the decrease in the absolute amount of the resin component in the film, it may be difficult to maintain the adhesion strength. Especially for resin materials used in such general applications, attention is paid to the adhesion strength of the film to the load in the vertical direction.

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

In order to achieve the subject of the invention, the inventors of the present invention have conducted intensive studies and found that: "By containing (A-1) glycidylamine epoxy resin and (B) liquid at 25°C in the resin composition The (meth)acrylic polymer can suppress the warpage of the cured product, and furthermore, the cured product film after the environmental test can have excellent adhesion to the load in the vertical direction", thus completing the present invention.

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

According to the present invention, it is possible to provide: a resin composition capable of suppressing the warpage of the cured product, and having excellent adhesion of the cured product film after an environmental test to the load in the vertical direction; a cured product of the above resin composition; including the above resin A resin sheet of the composition; a circuit board containing the cured product; a semiconductor chip package containing the cured product; and a semiconductor device provided with the semiconductor chip package.

[Best form to implement invention]

Hereinafter, the present invention will be explained based on its suitable embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily changed and implemented without departing from the scope of the present invention and its equivalent range.

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

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

The resin composition of the present invention may further include (A) epoxy resin, (B) (meth)acrylic polymer liquid at 25°C, (C) hardener, and (D) inorganic filler Contains any ingredients. Examples of optional components include (E) organic solvents and (F) other additives. Hereinafter, each component contained in the resin composition will be described in detail. ＜(A) Epoxy resin＞ The resin composition of the present invention contains (A) epoxy resin.

The content of the component (A) 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, the desired effect of the present invention is significantly obtained. 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 remarkably obtaining the desired effect of the present invention.

＜(A-1) Glycidylamine epoxy resin＞ (A) Component contains (A-1) glycidylamine type epoxy resin. The so-called (A-1) glycidylamine epoxy resin means an epoxy resin having at least one glycidylamine group and/or diglycidylamine group. The glycidylamino group contains one epoxy group, and the diglycidylamino group contains two epoxy groups. By using (A-1) glycidylamine 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 of the cured product can be improved. Humidity resistance.

(A-1) The glycidylamine type epoxy resin is preferably a bifunctional or more glycidylamine having two or more epoxy groups in a molecule from the viewpoint of obtaining a cured product excellent in heat resistance The type epoxy resin is also preferably a difunctional or trifunctional glycidylamine type epoxy resin having 2 or 3 epoxy groups in one molecule. Here, the epoxy group is not limited to those derived from a glycidylamino group and a diglycidylamino group, and may include those derived from a glycidyloxy group. When the non-volatile content of the glycidylamine type epoxy resin is set to 100% by mass, the ratio of the glycidylamine type epoxy resin having two or more functions is preferably 50% by mass from the viewpoint of improving the heat resistance of the cured product % Or more, more preferably 60% by mass or more, more preferably 70% by mass or more.

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

In this specification, the so-called alkylene group means a linear or branched divalent aliphatic saturated hydrocarbon group. The alkylene group having 1 to 10 carbon atoms is preferred, and the alkylene group having 1 to 5 carbon atoms is more preferred. Examples of the alkylene group include methylene, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group, and the like. There is no particular limitation.

(A-1) In the component, the glycidylamino group and the diglycidylamino group can be directly bonded to the aromatic ring. The aromatic ring system may have other substituents in addition to the glycidylamino group and the diglycidylamino group. Here, as other substituents, for example, a monovalent epoxy group-containing group, a monovalent hydrocarbon group, and the like can be mentioned. As a group containing a monovalent epoxy group, a glycidoxy group etc. are mentioned. As a monovalent hydrocarbon group, an alkyl group, an aryl group, etc. are mentioned, for example.

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

In this specification, the so-called aryl group means a monovalent aromatic hydrocarbon group. It is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl group, 2-anthryl group etc. are mentioned, for example.

(A-1) A component system may be used individually by 1 type, and may be used in combination of 2 or more types.

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

In formula (A-1), n each independently represents an integer of 0-4. Among them, n is preferably 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. Among them, m is preferably 1 or 2, more preferably 1.

In the formula (A-1), R ¹¹ each independently represents a monovalent epoxy group-containing group such as a glycidoxy group and a monovalent hydrocarbon group such as an alkyl group and an aryl group. When R ¹¹ is a glycidyloxy group, based on the bonding site of the nitrogen atom and the benzene ring, the R ^{11 is} preferably bonded to the para position. In addition, when R ¹¹ is an alkyl group, based on the bonding site of the nitrogen atom and the benzene ring, the R ^{11 is} preferably bonded to the ortho position.

In the formula (A-1), R ¹² represents a hydrogen atom or a 1- to 3-valent hydrocarbon group. As the divalent hydrocarbon group, an alkylene group, an arylene group, and the like can be mentioned. When m is 1, from the viewpoint of obtaining the desired effect of the present invention, R ¹² is preferably an alkyl group, and more preferably a methyl group. In addition, when m is 2, from the viewpoint that the desired effect of the present invention can be obtained, the R ¹² system is preferably an alkylene group, and more preferably a methylene group.

In this specification, the so-called aryl group means a divalent aromatic hydrocarbon group. It is preferably an arylene group having 6 to 14 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include phenylene group, naphthylene group, biphenylene group, and the like, and these bonding positions are not particularly limited.

Specific examples of the component (A-1) include "630" and "630LSD" manufactured by Mitsubishi Chemical Corporation (like the following formula (A-2)), and "EP-3980S" manufactured by ADEKA Corporation (like The following formula (A-3) is generally), "EP3950S", "EP3950L", "ELM-100", "ELM-100H", "ELM-434", "ELM-434L", etc. manufactured by Sumitomo Chemical Corporation. These systems may be used alone or in combination of two or more types.

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

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

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 remarkably obtaining the desired effect of the present invention , Preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, 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 remarkably obtaining the desired effect of the present invention.

The content of the (A-1) component relative to the total amount of the (A) component is not particularly limited, but when the (A) component in the resin composition is 100% by mass, the desired effect of the present invention is remarkably obtained From a standpoint, it is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more. The upper limit is not particularly limited, and may be, for example, 100% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less.

<Any epoxy resin other than (A-1) component> In addition to (A-1) glycidylamine-type epoxy resin, (A) epoxy resin may further contain other arbitrary epoxy resins. As other arbitrary epoxy resins, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type ring Oxygen resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic Epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane type epoxy resin, cyclohexane dimethanol type Epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of other arbitrary epoxy resins may be used alone, or two or more types may be used in combination.

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 standpoint of remarkably obtaining the desired effect of the present invention, the ratio of epoxy resins having two or more epoxy groups per molecule is relatively high relative to 100% by mass of the non-volatile content of other arbitrary epoxy resins. It is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Epoxy resins have epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as It is "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. It can also be used in combination with a liquid epoxy resin and a solid epoxy resin.

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

The liquid epoxy resin is preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol phenolic resin Varnish type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and epoxy resin having a butadiene structure.

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

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in a molecule, and an aromatic solid epoxy resin having 3 or more epoxy groups in a molecule is more preferable Epoxy resin.

The solid epoxy resin is preferably a dixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, and a dicyclopentadiene type epoxy resin. Resin, triphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, bisphenol AF type Epoxy resin, tetraphenylethane type epoxy resin.

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

If a combination of liquid epoxy resin and solid epoxy resin is used as any other epoxy resin, the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin/solid epoxy resin) The resin) is preferably 1 or more, more preferably 10 or more, particularly preferably 50 or more. By setting the mass ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the desired effect of the present invention can be remarkably obtained.

The epoxy equivalent of other arbitrary epoxy resins is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., more preferably 80g/eq.~2000g/eq. ., more preferably 110g/eq.~1000g/eq. By being in this range, the crosslinking density of the cured resin sheet will be sufficient, and an insulating layer with a small surface roughness can be provided. The epoxy equivalent is the mass of the resin per equivalent of epoxy group.

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

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

＜(B) Liquid (meth)acrylic polymer at 25℃＞ The resin composition of the present invention contains (B) a (meth)acrylic polymer that is liquid at 25°C. Here, the determination of the liquid state can be made according to the "Method of Confirming Liquid State" in Annex 2 of the Ministry's Order Concerning Testing and Properties of Dangerous Substances (Heisei First Year Autonomous Ministry Order No. 1). Still, the term "(meth)acrylic polymer" is a concept that includes both acrylic polymer and methacrylic polymer. The terms "(meth)acrylate" and "(meth)acrylamide" are also the same. The component (B) can play the role of alleviating stress in the cured resin composition.

The so-called (meth)acrylic polymer means a polymer formed by polymerizing monomer components including (meth)acrylate monomers. In addition to (meth)acrylate-based monomers, (meth)acrylic acid polymers can also include (meth)acrylamide-based monomers, styrene-based monomers, functional group-containing monomers, etc. Copolymerization component.

Examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) )Butyl acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate , Aliphatic (meth)acrylates such as tricyclodecyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, ( Aromatic (meth)acrylates such as phenoxypropyl meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (methyl) ) Alkoxy-based (meth)acrylates such as 3-methoxybutyl acrylate and 2-butoxyethyl (meth)acrylate; chloroethyl (meth)acrylate, three (meth)acrylate Halogenated (meth)acrylates such as fluoroethyl esters, etc.

Examples of (meth)acrylamide-based monomers include (meth)acrylamide, N-(n-butoxyalkyl)(meth)acrylamide, and N,N-dimethyl( Meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, etc. As a styrene-type monomer, styrene, α-methylstyrene, etc. are mentioned, for example.

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

Examples of monomers containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyethyl (meth)acrylate Hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (4-hydroxymethyl)cyclohexylmethyl (meth)acrylate, 2-(meth)acrylate Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, (methyl) ) 2-hydroxy-3-phenoxypropyl acrylate, 2,2-dimethyl-2-hydroxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl Group (meth)acrylamide and the like.

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

Furthermore, the (meth)acrylic polymer system may contain an alkoxysilyl group. Examples of alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl groups, triethoxysilyl groups, triisopropoxysilyl groups, and triphenoxysilyl groups; dimethoxysilyl groups Dialkoxysilyl groups such as methylsilyl group and diethoxymethylsilyl group; monoalkoxysilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group. These alkoxysilyl groups may be independent or may contain 2 or more types.

Specific examples of component (B) include "ARUFON UP-1000", "ARUFON UP-1010", "ARUFON UP-1020", "ARUFON UP-1021", and "ARUFON UP-1061" manufactured by Toagosei Co., Ltd. ”, “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 systems may 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, more preferably -20°C or lower, more preferably -40°C or lower, and particularly preferably -50°C or lower.

(B) The weight average molecular weight (Mw) of the component 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. It does not specifically limit as a lower limit, For example, it can be 100 mPa.s or more, 200 mPa.s or more, or 300 mPa.s or more.

The content of the component (B) 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, the desired effect of the present invention is significantly obtained from the viewpoint of 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 remarkably obtaining the desired effect of the present invention.

＜(C) Hardener＞ The resin composition of the present invention contains (C) a hardener. (C) The curing agent has the function of curing the (A) component.

(C) The curing agent is not particularly limited as long as it has the function of curing epoxy resin. Examples include phenolic curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, and benzene. Paraoxazine hardeners, cyanate ester hardeners, carbodiimide hardeners, phosphorus hardeners, amine hardeners, imidazole hardeners, guanidine hardeners, metal hardeners, etc. The hardener system may be used alone or in combination of two or more kinds. 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, and amine curing agents from the viewpoint of remarkably obtaining the desired effects of the present invention. Hardener and imidazole are a group of hardeners. In one embodiment, the (C) curing agent preferably includes an active ester curing agent.

As the phenol-based curing agent and the naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable. In addition, from the viewpoint of the adhesion to the adherend, a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent is preferred, and a phenolic curing agent containing a triazine skeleton or a triazine Naphthol hardener with oxazine skeleton. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenol novolak resin containing a triazine skeleton is preferred. Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" and Nippon Kayaku made by Meiwa Chemical Co., Ltd. "NHN", "CBN", "GPH" manufactured by the company, "SN-170", "SN-180", "SN-190", "SN-475", "SN- 485", "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P" manufactured by DIC , "LA-1356", "TD2090", "TD-2090-60M", etc.

As the acid anhydride-based curing agent, a curing agent having one or more acid anhydride groups in one molecule is mentioned. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene Tetracarboxylic dianhydride, oxodiphthalic dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro -5-(Tetrahydro-2,5-dioxo-3-furyl)-naphthalene[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydro trimellitate) , Polymeric acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid. Examples of commercially available products of acid anhydride hardeners include "HNA-100" and "MH-700" manufactured by Nippon Rika Corporation.

The active ester curing agent is not particularly limited, but it is generally preferable to have two or more reactions in a molecule such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxyl compounds. Compounds with high activity of ester groups. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and one obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Active ester hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxyl Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac Wait. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing 1 molecule of dicyclopentadiene with 2 molecules of phenol.

Specifically, it is preferably an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound having a naphthalene structure, an active ester compound containing an acetyl compound of a phenol novolak, and a benzyl containing a phenol novolak. Among the active ester compounds of the amide compound, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The so-called "dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit composed of phenylene-pentalene-phenylene.

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

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "HFB2006M" manufactured by Showa Polymer Corporation and "HFB2006M" manufactured by Shikoku Chemical Industry Co., Ltd. Pd", "Fa", etc.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4' -Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis (4-cyanate ester) phenyl propane, 1,1-bis (4-cyanate ester phenyl methane), bis (4-cyanate ester-3,5-dimethylphenyl) methane, 1, 3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl)ether, etc. The bifunctional cyanate ester resins, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, and prepolymers obtained by triazineizing a part of these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate resin) manufactured by LONZA Japan, "BA230", and "BA230S75" (double Part or all of the phenol A dicyanate is triazineized to form a trimer (prepolymer) and the like.

As specific examples of the carbodiimide-based curing agent, "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd. can be cited.

Examples of phosphorus-based hardeners include triphenyl phosphine, boric acid phosphonium compounds, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium caprate, ( 4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate and the like.

As the amine curing agent, for example, triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6,-shen (dimethyl Aminomethyl) phenol, 1,8-Diazirbicyclo(5,4,0)-undecene, etc., 4-Dimethylaminopyridine, 1,8-Diazabicyclo(5,4, 0)-Aliphatic amine hardeners such as undecene; benzidine, o-tolidine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3' -Dimethyldiphenylmethane ("KAYABOND C-100" manufactured by Nippon Kayaku as a commercial product), 4,4'-diamino-3,3'-diethyldiphenylmethane (as Commercially available Nippon Kayaku "KAYAHARD AA"), 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane (as a commercially available Nippon Kayaku "KAYABOND C-200S"), 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane ("KAYABOND C" manufactured by Nippon Kayaku as a commercial product -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-phenylene bis(1-methyl -Ethylene)] bisaniline (as a commercially available product "Dianiline M" manufactured by Mitsui Chemicals), 4,4'-[1,4-phenylenebis(1-methyl-ethylene)] Dianiline (as a commercially available product "Dianiline P" manufactured by Mitsui Chemicals), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (as a commercially available product, manufactured by Wakayama Seiki "BAPP"), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)biphenyl and other aromatics Group amine hardener.

Examples of imidazole-based hardeners include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 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, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate , 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecane Alkyl imidazolyl-(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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2- Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a]benzimidazole , 1-Dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resin .

A commercially available product can be used as the imidazole-based hardener system, and for example, "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd. can be mentioned.

As the guanidine curing agent, for example, dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, metformin Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazbicyclo[4.4.0]dec-5-ene, 7-methyl-1, 5,7-Triazbicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1, 1-Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc.

Examples of metal-based hardeners include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt acetylpyruvate (II) and cobalt acetylpyruvate (III), and organic copper such as copper acetylpyruvate (II). Complexes, organic zinc complexes such as zinc acetopyruvate (II), organic iron complexes such as iron (III) acetopyruvate, and organic nickel complexes such as nickel (II) acetopyruvate Manganese (II) acetylpyruvate and other organic manganese complexes. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the hardener is included, the ratio of the amount of epoxy resin to hardener is based on the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener], preferably 1:0.2~ The range of 1:2 is more preferably 1:0.3~1:1.5, and more preferably 1:0.4~1:1.2. Here, the so-called reactive groups of the curing agent refer to active hydroxyl groups, active ester groups, etc., which vary depending on the type of curing agent. In addition, the so-called total number of epoxy groups of epoxy resin refers to the total value of the value obtained by dividing the mass of the non-volatile content of each epoxy resin by the epoxy equivalent for all epoxy resins; the so-called curing The total number of reactive groups of the agent refers to the total value of the value obtained by dividing the mass of the non-volatile content of each curing agent by the equivalent of the reactive group for all curing agents. By setting the ratio of the amount of the epoxy resin to the curing agent in the above range, the heat resistance of the obtained cured product can be further improved.

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

＜(D)Inorganic fillers＞ 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 include silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite , Gibbsite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanic acid Magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium phosphotungstate, etc., are particularly suitable for silica and alumina. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Moreover, as the silica, spherical silica is preferable. (D) The inorganic filler system may be used alone or in combination of two or more kinds.

(D) Commercial products of inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; and "SP507-05" manufactured by Admatechs. "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; "Shirufiru NSS-3N", "Shirufiru NSS-4N", "Shirufiru NSS" manufactured by Tokuyama -5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", etc. 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, and more preferably It is 15 μm or less, particularly preferably 10 μm or less. The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.1 μm or more, more preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. The average particle size of the inorganic filler can be measured by the laser diffraction-scattering method based on the Mie scattering theory. Specifically, a laser diffraction scattering type particle size distribution measuring device can be used to produce the particle size distribution of the inorganic filler on a volume basis, and the median particle size can be measured as the average particle size. The measurement sample can be obtained by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial, and dispersing it for 10 minutes by ultrasonic waves. For the measurement sample, a laser diffraction particle size distribution measuring device is used, the wavelength of the light source is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured by the flow cell method. The particle size distribution calculates the average particle size as the median particle size. As a laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

From the viewpoint of improving moisture resistance and dispersibility, it is preferable to use aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, alkoxysilane compound, organosilazane compound, titanic acid (D) Inorganic filler is processed by one or more surface treatment agents, such as an ester coupling agent. Commercial products of surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (Long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-form Propylene oxypropyl trimethoxysilane), "KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment by the surface treatment agent is preferably set to 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 a surface treatment agent of 0.2% to 5% by mass, preferably 0.2% to 3% by mass, preferably 0.3% by mass %~2% by mass for surface treatment.

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. The amount of carbon per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, more preferably 0.2 mg/m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity in the form of a sheet from increasing, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and more preferably 0.5 mg /m ² or less.

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

(D) The specific surface area of the inorganic filler, from the viewpoint of further enhancing the effect of the present invention, 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 above. Although the upper limit is not particularly limited, it 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 is obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the sample surface 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 the non-volatile components in the resin composition are 100% by mass, from the viewpoint of use in a specific application, 20% by mass is preferable Above, it is 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 may be, for example, 98% by mass or less, 95% by mass or less, 92% by mass or less, 90% by mass or less.

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

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol Ester solvents such as alcohol acetate, diethylene glycol ethyl ether acetate, γ-butyrolactone; cellosolve and carbitol solvents such as butyl carbitol; benzene, toluene, xylene, ethyl Aromatic hydrocarbon solvents such as benzene and trimethylbenzene; amine solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; methanol, ethanol, 2 -Alcohol solvents such as methoxypropanol; hydrocarbon solvents such as cyclohexane and methylcyclohexane. An organic solvent system can be used individually by 1 type, and can also be used combining 2 or more types at arbitrary ratios.

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 optional components. Examples of such additives include organic fillers, thickeners, defoamers, leveling agents, adhesion imparting agents, polymerization initiators, flame retardants, and the like. These additives may be used alone or in combination of two or more types. The respective content can be appropriately set by a person having ordinary knowledge in the relevant technical field.

＜Method of manufacturing resin composition＞ In one embodiment, the resin composition system of the present invention can be manufactured by a method including the following steps. The foregoing steps are, for example, in a reaction vessel, in any order and/or part or all of them are added simultaneously ( A) Epoxy resin, (B) (meth)acrylic polymer that is liquid at 25°C, (C) hardener, (D) inorganic filler, (E) organic solvent and other required (F) Other additives are mixed to obtain a resin composition.

In the above steps, the temperature of the process of adding each component can be appropriately set, and during the process of adding each component, heating and/or cooling can be performed temporarily or throughout the process. In the process of adding each ingredient, stirring or shaking can be carried out. Moreover, after the above-mentioned step, it is preferable to further include a step of stirring the resin composition to uniformly disperse it using a stirring device such as a stirrer.

＜Characteristics of resin composition＞ Since the resin composition of the present invention contains (A) epoxy resin, (B) (meth)acrylic polymer liquid at 25°C, (C) hardener and (D) inorganic filler, and (A) The component contains (A-1) a glycidylamine type epoxy resin, so that the warpage of the cured product can be suppressed, and the cured product film after the environmental test can be obtained with excellent adhesion to the load in the vertical direction. Furthermore, in one embodiment, the resin composition system of the present invention can suppress the generation of flow marks.

In one embodiment, the cured layer of the resin composition of the present invention (thickness: 300μm; heated at 180°C for 90 minutes for thermal curing) and a substrate composed of a 12-inch silicon wafer, according to the Electronic Information Technology Industry Association The amount of warpage measured by the JEITA EDX-7311-24 of the specification at 25°C 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 cured product layer (thickness 50μm; heated at 180°C for 90 minutes for thermal curing) of the resin composition of the present invention after a high-temperature and high-humidity environment test (130°C and 85% RH for 96 hours) affects the silicon wafer Adhesive strength, when the vertical tensile test is carried out at 0.1Kg/sec, it is preferably 300Kgf/cm ² or more, more preferably 400Kgf/cm ² or more, more preferably 450Kgf/cm ² or more, particularly preferably 500Kgf/ cm ² or more.

＜Use of resin composition＞ Due to the above-mentioned advantages, the cured product of the resin composition of the present invention is useful for sealing layers and insulating layers of semiconductors. Therefore, this resin composition system can be used as a resin composition for semiconductor sealing or an 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 an insulating layer of a semiconductor chip package) and for forming a circuit board (including a printed wiring board). ) The resin composition of the insulating layer (resin composition for the insulating layer of the circuit board).

In addition, for example, the resin composition system of the present invention can be suitably used as a resin composition for sealing a semiconductor wafer of a semiconductor chip package (a resin composition for sealing a semiconductor wafer).

As a semiconductor chip package to which a sealing layer or an insulating layer formed of the cured resin composition of the present invention can be applied, 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), Fan-in type PLP.

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

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

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

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

In addition, the thickness of the cured product obtained by curing the resin composition layer is preferably 1 μm or more and 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 a film made of a plastic material, metal foil, and release paper, and a film made of a plastic material or metal foil is preferred.

When a film made of a plastic material is used as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate (hereinafter referred to as " PEN") and other polyesters; polycarbonate (hereinafter referred to as "PC"); polymethyl methacrylate (hereinafter referred to as "PMMA") and other acrylic polymers; 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. As the copper foil system, a foil composed of a simple metal containing copper can also be used, or a foil composed of an alloy containing copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) .

For the support system, polishing treatment, corona treatment, anti-static treatment, etc., can be applied to the surface joined with the resin composition layer.

Moreover, as a support system, the support body with a mold release layer which has a mold release layer on the surface joined with a resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. More than one kind of release agent. As a commercially available product of the mold release agent, for example, "SK-1", "AL-5", "AL-7", etc., manufactured by Lintec, which are alkyd resin-based mold release agents, can be mentioned. In addition, examples of the support with a release layer include "Lumirror T60" manufactured by Toray Corporation; "PUREX" manufactured by Teijin Corporation; "Unipeel" manufactured by Unitika Corporation.

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. Furthermore, when using a support with a mold release layer, it is preferable that the thickness of the whole support with a mold release layer is the said range.

A coating device such as a die coater can be used to coat the resin composition on the support to produce a resin sheet. In addition, the resin composition can be dissolved in an organic solvent to prepare a resin varnish as needed, and the resin varnish can be applied to produce a resin sheet. By using a solvent to adjust the viscosity, the coatability can be improved. When a resin varnish is used, the resin varnish is usually dried after coating to form a resin composition layer.

The drying system can be implemented by a well-known method 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, and it is preferable to dry it so that it becomes 5% by mass or less. It depends on the boiling point of the organic solvent in the resin varnish. For example, if a resin varnish containing 30% by mass to 60% by mass of organic solvent is used, it can be dried at 50°C to 150°C for 3 minutes to 10 minutes. , Thereby forming a resin composition layer.

The resin sheet may include any layer other than the support and the resin composition layer as required. For example, in the resin sheet, the surface that is not joined to the support of the resin composition layer (that is, the surface opposite to the support) may be matched with the support to provide a protective film. The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film prevents impurities and the like from adhering to or scratching the surface of the resin composition layer. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, the resin sheet can be wound into a cylindrical form for storage.

When manufacturing a semiconductor chip package, the resin sheet system can be suitably used for forming an insulating layer (resin sheet for insulation of a semiconductor chip package). For example, a resin sheet can be used for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board). Examples of packages using such a substrate include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

Moreover, the resin sheet system can be suitably used for sealing a semiconductor wafer (resin sheet for semiconductor wafer sealing). Examples of applicable semiconductor chip packages include Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP, and the like.

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

Furthermore, the resin sheet system can be used in other wide-ranging applications requiring high insulation reliability. For example, a resin sheet system can be suitably used for forming an insulating 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) The step of thermally curing the resin composition layer to form an insulating layer.

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

In addition, a conductor layer may be formed on one or both surfaces of the base material. In the following description, a substrate containing a substrate and a conductor layer formed on the surface of the substrate is appropriately referred to as "a substrate with a wiring layer". As the conductor material contained in the conductor layer, for example, it includes a group selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. A group of more than one metal material. As the conductor material system, a simple metal or an alloy can be used. Examples of alloys include alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of the versatility of the conductor layer formation, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as the elemental metal is preferred; and Alloys of nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys. Among them, elemental metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel-chromium alloys are preferred; elemental metals of copper are particularly preferred.

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

The thickness of the conductor layer may vary 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, particularly preferably 15 μm to 20 μm.

The conductor layer can be formed by a method including, for example, the following steps: laminating a dry film (photoresist film) on a substrate; using a photomask to expose and develop the dry film under specified conditions to form a pattern The step of forming a patterned dry film; using the developed patterned dry film as a plating mask and forming a conductor layer by a plating method such as electrolytic plating; and peeling off the patterned dry film的步。 The steps. As the dry film, a photosensitive dry film composed of a photoresist composition can be used. For example, a dry film formed of a resin such as a novolak resin and an acrylic resin can be used. The lamination conditions of the base material and the dry film can be the same as the lamination conditions of the base material and the resin sheet described later. The peeling system of a dry film can be implemented using alkaline peeling liquid, such as a sodium hydroxide solution.

After preparing the substrate, a resin composition layer is formed on the substrate. When a conductive layer is formed on the surface of the base material, the formation of the resin composition layer is preferably performed by embedding the conductive layer in the resin composition layer.

The formation of the resin composition layer can be performed, for example, by laminating a resin sheet and a substrate. This lamination system can be performed by, for example, heating and pressing the resin sheet on the substrate from the support side so that the resin composition layer is bonded to the substrate. As a member for heat-pressing the resin sheet on the base material (hereinafter sometimes referred to as "heating and pressing member"), for example, a heated metal plate (SUS mirror plate or the like) or metal roller (SUS roller or the like) can be mentioned. However, instead of directly pressing the heating and pressing member on the resin sheet, it is preferable to press the resin sheet to fully follow the surface irregularities of the substrate, and to press through an elastic material such as a heat-resistant rubber.

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

After the lamination, under normal pressure (under atmospheric pressure), for example, the heating and pressing member is pressed from the support side, so that the layered resin sheet can be smoothed. The pressing conditions of the smoothing treatment can be set to the same conditions as the heating and pressing conditions of the above-mentioned lamination. Still, the lamination and smoothing process can be continuously performed using a vacuum laminator.

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

After the resin composition layer is formed on the substrate, the resin composition layer is thermally cured to form an insulating layer. Although the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, and more preferably 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 thermally cured, the resin composition layer may be subjected to a preliminary heating treatment for heating at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally cured, the resin composition can usually be made at a temperature of 50°C or more but less than 120°C (preferably 60°C or more and 110°C or less, and preferably 70°C or more and 100°C or less). The layer is usually preheated for more than 5 minutes (preferably 5 minutes to 150 minutes, and more preferably 15 minutes to 120 minutes).

With the above operations, a circuit board with an insulating layer can be manufactured. Moreover, the manufacturing method of a circuit board may further include arbitrary steps. For example, when a resin sheet is used to manufacture a circuit board, the method of manufacturing the circuit board may include a step of peeling the support of the resin sheet. The support system may be peeled before the thermal curing of the resin composition layer, or may be peeled after the thermal curing of the resin composition layer.

The manufacturing method of the circuit board may include, for example, the following steps: after forming the insulating layer, polishing the surface of the insulating layer. The polishing method is not particularly limited. The surface of the insulating layer can be polished using, for example, a flat grinding disc.

The manufacturing method of the circuit board may include, for example, the step (3) of interlayer connection of the conductor layer, that is, the so-called step of opening holes in the insulating layer. Accordingly, holes such as through holes and through holes can be formed on the insulating layer. Examples of the formation method of the through hole include laser irradiation, etching, mechanical drilling, and the like. The size or shape of the through hole can be appropriately determined according to the design of the circuit substrate. Furthermore, in step (3), the interlayer connection can be made by grinding or grinding the insulating layer.

After the through hole is formed, it is preferable to perform the step of removing the glue residue in the through hole. This step is called the desmear step. For example, when the conductive layer is formed on the insulating layer by a plating step, the through hole may be subjected to a wet desmear treatment. Furthermore, when the conductor layer is formed on the insulating layer by a sputtering step, a dry desmear step such as a plasma treatment step can be performed. Furthermore, roughening treatment can also be applied to the insulating layer through the desmear removal step.

Furthermore, before forming the conductor layer on the insulating layer, the insulating layer may be roughened. According to this roughening treatment, the surface of the insulating layer including the through hole is usually roughened. As the roughening treatment system, any roughening treatment of dry type and wet type can be performed. As an example of dry roughening treatment, plasma treatment etc. are mentioned. In addition, as an example of the wet roughening treatment, a method of sequentially performing a swelling treatment by a swelling liquid, a roughening treatment by an oxidizing agent, and a neutralization treatment by a neutralization liquid can be mentioned.

After the through holes are formed, a conductive layer can be formed on the insulating layer. By forming the conductor layer at the position where the through hole is formed, the newly formed conductor layer can be electrically connected to the conductor layer on the surface of the base material for interlayer connection. The formation method of the conductor layer may, for example, be a plating method, a sputtering method, a vapor deposition method, etc., and among them, a plating method is preferred. In a suitable embodiment, the surface of the insulating layer is plated by a suitable method such as a semi-additive method and a full-additive method to form a conductor layer having a desired wiring pattern. Moreover, if the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the formed conductor layer may be a simple metal or an alloy. In addition, the conductor layer may have a single-layer structure or a multilayer structure including two or more layers of different types of materials.

Here, an example of an embodiment in which a conductor layer is formed on an insulating layer will be described in detail. A plating seed layer is formed by electroless plating on the surface of the insulating layer. Next, a mask pattern is formed on the formed plating seed layer in a manner corresponding to the desired wiring pattern to expose a part of the plating seed layer. On the exposed plating seed layer, an electrolytic plating layer is formed by electrolytic plating, and then the mask pattern is removed. After that, the unnecessary plating seed layer is removed by processing such as etching, and a conductor layer having a desired wiring pattern can be formed. In addition, when forming the conductor layer, the dry film used for the formation of the mask pattern is the same as the above dry film.

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

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

The bonding conditions between the circuit board and the semiconductor wafer may be any conditions under which the terminal electrodes of the semiconductor wafer and the circuit wiring of the circuit board can be connected by conductors. For example, conditions used in flip chip mounting of semiconductor wafers can be used. In addition, for example, between a semiconductor wafer and a circuit board, an insulating adhesive may be interposed for bonding.

As an example of the bonding method, a method of pressing a semiconductor wafer to a circuit board can be cited. As the 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 1 The range of seconds to 60 seconds (preferably 5 seconds to 30 seconds).

In addition, as another example of the bonding method, a method of performing reflow to bond the semiconductor wafer to the circuit board can be cited. The reflux conditions can be set in the range of 120°C to 300°C.

After the semiconductor wafer is bonded to the circuit board, the semiconductor wafer can be filled with a molded underfill material. As the molded underfill material, the above-mentioned resin composition can be used, and the above-mentioned resin sheet can be used.

The semiconductor chip package according to the second embodiment of the present invention includes a semiconductor chip and a cured product of the aforementioned resin composition that seals the semiconductor chip. In such a semiconductor chip package, generally, the cured product of the resin composition functions as a sealing layer. As the semiconductor chip package related to the second embodiment, for example, a Fan-out type WLP can be cited.

The manufacturing method of such a semiconductor chip package includes the following steps: (A) The step of laminating a temporary fixing film on the substrate; (B) The step of temporarily fixing the semiconductor wafer on the temporary fixing film; (C) The step of forming a sealing layer on the semiconductor wafer; (D) The step of peeling the substrate and the temporary fixing film from the semiconductor wafer; (E) A step of forming a rewiring forming layer as an insulating layer on the peeled surface of the substrate of the semiconductor wafer and the temporary fixing film; (F) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer; and (G) a step of forming a solder resist layer on the rewiring layer. In addition, the aforementioned method for manufacturing a semiconductor chip package may also include (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces.

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

Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold rolled steel plates (SPCC); and FR-4 substrates such as glass fiber infiltrating epoxy resin, etc. And a substrate obtained by thermal curing treatment; a substrate composed of bismaleimide triazine resin such as BT resin.

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

(Step (B)) Step (B) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. For the temporary fixing of the semiconductor wafer, a device such as a flip chip bonder or a die bonder can be used. The arrangement layout and number of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, and the number of production of semiconductor chip packages for the purpose. For example, the semiconductor wafer can be temporarily fixed by aligning the semiconductor wafer in a matrix of plural rows and plural columns.

(Step (C)) Step (C) is a step of forming a sealing layer on the semiconductor wafer. The sealing layer is formed by a cured product of the above-mentioned resin composition. In general, the sealing layer is formed by a method including the steps of forming a resin composition layer on a semiconductor wafer, and thermally curing the resin composition layer to form the sealing layer.

The excellent compression moldability of the resin composition is utilized, and the resin composition layer is preferably formed by the compression molding method. In general, the compression molding method is to arrange a semiconductor wafer and a resin composition in a mold, and apply pressure to the resin composition in the mold and apply heat as required to form a resin composition layer covering the semiconductor wafer.

The specific operation system of the compression molding method can be as follows, for example. As a mold for compression molding, an upper mold and a lower mold are prepared. Furthermore, the resin composition is applied to the semiconductor wafer temporarily fixed on the temporary fixing film as described above. The semiconductor wafer coated with the resin composition is fixed to the lower mold together with the substrate and the temporary fixing film. After that, the upper mold and the lower mold are closed, and heat and pressure are applied to the resin composition to perform compression molding.

In addition, the specific operation of the compression molding method may be performed in the following manner, for example. As a mold for compression molding, an upper mold and a lower mold are prepared. The resin composition is placed on the lower mold. In addition, the semiconductor wafer is fixed to the upper mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are clamped in such a manner that the resin composition placed on the lower mold is in contact with the semiconductor wafer fixed on the upper mold, and heat and pressure are applied to perform compression.

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 temperature of the mold during molding is preferably a temperature that can exhibit the excellent compression moldability of the resin composition, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, and preferably 200°C Hereinafter, it is more preferably 170°C or lower, and particularly preferably 150°C or lower. In addition, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, preferably 50 MPa or less, more preferably 30 MPa or less, particularly preferably 20 MPa or less. 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, the mold can be removed after the formation of the resin composition layer. The removal of the mold may be performed before the thermal curing of the resin composition layer, or may be performed after the thermal curing.

The formation of the resin composition layer can be carried out by laminating a resin sheet and a semiconductor wafer. For example, by heating and pressing the resin composition layer of the resin sheet and the semiconductor wafer, the resin composition layer can be formed on the semiconductor wafer. The lamination of the resin sheet and the semiconductor wafer can generally be carried out in the same manner as the lamination of the resin sheet and the base material in the circuit board manufacturing method, and the semiconductor wafer can be used instead of the base material.

After the resin composition layer is formed on the semiconductor wafer, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor wafer. According to this, the semiconductor wafer can be sealed by the cured product of the resin composition. The thermosetting conditions of the resin composition layer may be the same as the thermosetting conditions of the resin composition layer in the method of manufacturing a circuit board. Furthermore, before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preliminary heating treatment for heating at a temperature lower than the curing temperature. The processing conditions of this preliminary heat treatment can be the same conditions as those of the preliminary heat treatment in the circuit board manufacturing method.

(Step (D)) Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor wafer. The peeling method is suitable to adopt a suitable method according to the material of the temporary fixing film. As the peeling method, for example, a method of peeling the temporarily fixed film by heating, foaming or expanding it. In addition, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through the substrate to reduce the adhesive force of the temporary fixing film and then peeling.

In the method of heating, foaming, or expanding and peeling the temporarily fixed film, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of irradiating ultraviolet rays to reduce the adhesive force of the temporarily fixed film and then peeling off, the amount of ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

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

As the material of the rewiring forming layer, any material having insulating properties can be used. Among them, from the viewpoint of the ease of manufacture of the semiconductor chip package, photosensitive resin and thermosetting resin are preferred. In addition, as the thermosetting resin, the resin composition of the present invention can be used.

After the rewiring forming layer is formed, in order to connect the semiconductor wafer and the rewiring layer forming layer, via holes may be formed in the rewiring forming layer.

If the material of the redistribution forming layer is a photosensitive resin, generally speaking, the formation method of the via hole is to irradiate the surface of the redistribution forming layer with active energy rays through a mask pattern to make the redistribution forming layer of the irradiated part Perform light hardening. Examples of the active energy rays include ultraviolet rays, visible rays, electron rays, X-rays, etc., and ultraviolet rays are particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. As the exposure method, for example, a contact exposure method in which a mask pattern is adhered to the redistribution forming layer and then exposed; a non-contact exposure method in which the mask pattern is adhered to the redistribution forming layer and using parallel light for exposure Contact exposure method, etc.

After the redistribution forming layer is photocured, the redistribution forming layer is developed and the unexposed parts are removed to form via holes. The development system can use either wet development or dry development. Examples of the development method include a dipping method, a mixing method, a spray method, a brushing method, a blade coating method, etc., and the mixing method is suitable from the viewpoint of analysis.

When the material of the redistribution forming layer is a thermosetting resin, the method of forming the via hole may include, for example, laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is preferred. The laser irradiation system can be performed using an appropriate laser processing machine using light sources such as carbon dioxide lasers, UV-YAG lasers, and excimer lasers.

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

(Step (F)) Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring forming layer can be the same method as the method of forming the conductor layer on the insulating layer in the manufacturing method of the circuit board. In addition, step (E) and step (F) may be repeated to form a rewiring layer and a rewiring forming layer to be alternately stacked (buildup).

(Step (G)) Step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any material having insulating properties can be used. Among them, from the viewpoint of the ease of manufacture of the semiconductor chip package, photosensitive resin and thermosetting resin are preferred. Moreover, as a thermosetting resin, the resin composition of this invention can be used.

In addition, in step (G), bump processing to form bumps can be performed as needed. The bump processing system can be performed by methods such as solder balls and solder plating. In addition, the formation of through holes in bump processing can be performed in the same manner as in step (E).

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

＜Semiconductor device＞ The semiconductor device includes a semiconductor chip package. Examples of semiconductor devices include electrical products (such as computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (such as motorcycles, automobiles, and trams). , Ships, airplanes, etc.) and other semiconductor devices. [Example]

Hereinafter, the present invention will be described in detail with examples. The present invention is not limited to these embodiments. However, the "parts" and "%" which indicate the quantity below, unless otherwise specified, have the meanings of "parts by mass" and "% by mass" respectively.

<Example 1> Two parts of glycidylamine epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115g/eq.) and 2 parts of glycidylamine epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, epoxy equivalent 95g/eq.) eq.) 3 parts, liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd., viscosity (25°C) 500mPa.s, Mw2,000, Tg-80°C) 1 part, bisphenol A epoxy resin ("EXA-850CRP" manufactured by DIC, epoxy equivalent 170~175g/eq.) 6 parts, acid anhydride hardener ("HNA-100" manufactured by New Japan Rika Co., Ltd., acid anhydride equivalent 179g/eq.) 6 parts, dioxide 83 parts of silicon A, 0.1 part of imidazole hardener ("2E4MZ" manufactured by Shikoku Kasei Co., Ltd., 2-ethyl-4-methylimidazole) were uniformly dispersed using a mixer to prepare a resin composition.

<Example 2> In addition to using 1 part of liquid acrylic polymer ("UG-4010" manufactured by Toagosei Co., Ltd., viscosity (25°C) 3,700mPa.s, Mw 2,900, Tg-57°C), instead of liquid acrylic polymer (Toagosei The resin composition was prepared in the same manner as in Example 1 except for 1 part made by the company ("UP-1020").

<Example 3> In addition to using 1 part of liquid acrylic polymer (Toagosei "US-6100", viscosity (25°C) 2,300 mPa.s, Mw 2,500, Tg-58°C), instead of liquid acrylic polymer (Toagosei The resin composition was prepared in the same manner as in Example 1 except for 1 part made by the company ("UP-1020").

<Example 4> One part of glycidylamine epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115g/eq.), and 1 part of glycidylamine epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, epoxy equivalent 95g/eq.) eq.) 10 parts, liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd., viscosity (25°C) 500mPa.s, Mw2,000, Tg-80°C) 1 part, bisphenol A epoxy resin (DIC company "EXA-850CRP", epoxy equivalent 170~175g/eq.) 6 parts, phenolic hardener (Meiwa Chemicals "MEH-8000H") 1 part, silicon dioxide A83 parts, imidazole hardener ("2E4MZ" manufactured by Shikoku Chemical Co., Ltd., 2-ethyl-4-methylimidazole) 0.4 parts, uniformly dispersed with a mixer to prepare a resin composition.

<Example 5> Except for using 1 part of amine hardener ("KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd.) instead of 1 part of phenolic hardener ("MEH-8000H" manufactured by Meiwa Kasei), the rest is the same as in Example 4. Method to prepare the resin composition.

<Example 6> Except that 95 parts of aluminum oxide A was used instead of 83 parts of silicon dioxide A, the rest was used in the same manner as in Example 1 to prepare the resin composition.

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

<Example 8> 4 parts of glycidylamine epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115g/eq.) and 4 parts of glycidylamine epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, epoxy equivalent 95g/eq.) eq.) 9 parts, liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd., viscosity (25°C) 500mPa.s, Mw2,000, Tg-80°C), 1 part, acid anhydride hardener (Nippon Rika "HNA-100" manufactured by the company, anhydride equivalent of 179g/eq.) 4 parts, 83 parts of silicon dioxide A, imidazole hardener ("2E4MZ" manufactured by Shikoku Chemical Co., Ltd., 2-ethyl-4-methylimidazole) 0.1 The portion is uniformly dispersed using a mixer to prepare a resin composition.

<Example 9> One part of glycidylamine epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115g/eq.), and 1 part of glycidylamine epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, epoxy equivalent 95g/eq.) eq.) 1 part, liquid acrylic polymer ("UP-1020" manufactured by Toagosei Co., Ltd., viscosity (25°C) 500mPa.s, Mw2,000, Tg-80°C) 1 part, bisphenol A epoxy resin ("EXA-850CRP" manufactured by DIC, epoxy equivalent 170~175g/eq.) 9 parts, acid anhydride hardener ("HNA-100" manufactured by New Japan Rika Co., Ltd., acid anhydride equivalent 179g/eq.) 6 parts, dioxide 83 parts of silicon A, 0.1 part of imidazole hardener ("2E4MZ" manufactured by Shikoku Kasei Co., Ltd., 2-ethyl-4-methylimidazole) were uniformly dispersed using a mixer to prepare a resin composition.

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

<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 filler used> Silica A: average particle size 6.0μm, maximum cut-off particle size 20μm, specific surface area 4.8m ² /g, tested by KBM573(N-phenyl-3-aminopropyltrimethoxysilane , Shin-Etsu Chemical Co., Ltd.) processed spherical silicon dioxide. Alumina A: average particle size 4.8um, maximum cut-off particle size 24um, specific surface area 2.7m ² /g, treated with KBM573 (N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) Of spherical alumina.

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

<Test Example 2: Evaluation of Appearance> The appearance of the resin layer of the sample substrate prepared in Test Example 1 was observed. If the area occupied by the flow marks in the entire resin layer surface is less than 20%, it is evaluated as "〇"; if it exceeds 20%, it is evaluated as "△".

<Test Example 3: Adhesion Evaluation after High Temperature and High Humidity Environmental Test (HAST)> Using the sample substrate produced in Test Example 1, a high temperature and high humidity environmental test (HAST) was performed under conditions of 130°C and 85% RH for 96 hours. The cured product after HAST was polished using #180 sandpaper until the resin layer had a thickness of 50 μm. The polished sample was cut into a test piece with a width of 1 cm square. For the resin layer, a 2.7mm φ2.7mm adhesive-attached stud pin was made to stand perpendicular to the resin layer and heated at 150°C for 60 minutes to produce a stud pin Test piece attached to the resin layer. The obtained test piece with stud pin was measured for a vertical tensile test at a test rate of 0.1 kg/sec using a vertical tensile testing machine ROMULUS manufactured by QUAD GROUP. Measure 5 test pieces and calculate the average value. If the adhesion strength exceeds 500Kgf/cm ² , it is evaluated as "○", and if it is less than 500Kgf/cm ^{2 it} is evaluated as "×".

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

Based on the above results, it can be seen that when (A-1) glycidylamine epoxy resin and (B) (meth)acrylic polymer liquid at 25°C are used, the warpage of the cured product can be suppressed. In addition, the cured film after the environmental test can achieve excellent adhesion to the load in the vertical direction.

Claims (16)

A resin composition containing (A) epoxy resin, (B) (meth)acrylic polymer liquid at 25°C, (C) hardener, and (D) inorganic filler, (A) component contains (A-1) Glycidylamine type epoxy resin. The resin composition of claim 1, wherein the component (A-1) is a bifunctional or trifunctional glycidylamine epoxy resin. The resin composition of claim 1, wherein when the non-volatile components other than component (D) in the resin composition are set to 100% by mass, the content of component (A-1) is 20% by mass or more and 80% by mass the following. The resin composition of claim 1, wherein when the non-volatile components other than the component (D) in the resin composition are set to 100% by mass, the content of the component (B) is 0.5% by mass to 20% by mass. The resin composition of claim 1, wherein the component (C) is selected from the group consisting of phenolic hardeners, naphthol hardeners, acid anhydride hardeners, amine hardeners, and imidazole hardeners. Agent. The resin composition according to claim 1, wherein when all the non-volatile components in the resin composition are 100% by mass, the content of the component (D) is 70% by mass or more. The resin composition of claim 1, which is used to form an insulating layer of a semiconductor chip package. The resin composition of claim 1, which is used to form an insulating layer of a circuit board. The resin composition of claim 1, which is used to seal a semiconductor chip of a semiconductor chip package. A hardened product of the resin composition according to any one of claims 1 to 9. A resin sheet having a support body and a resin composition layer provided on the support body, the resin composition layer comprising the resin composition according to any one of claims 1-9. A circuit board comprising an insulating layer formed by a cured product of the resin composition as claimed in any one of claims 1 to 9. A semiconductor chip package including the circuit substrate of claim 12 and a semiconductor chip mounted on the circuit substrate. A semiconductor device provided with the semiconductor chip package according to claim 13. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 9 for sealing the semiconductor chip. A semiconductor device provided with the semiconductor chip package according to claim 15.