KR20200104237A - Resin composition - Google Patents

Abstract

The present invention provides a resin composition that can prevent a cured product from warping and has excellent adhesion to weighting in a vertical direction of a cured product thin film after an environmental test. The resin composition contains (A) an epoxy resin, (B) a liquid methacrylic polymer at 25°C, (C) a curing agent and (D) an inorganic filler, wherein the component (A) contains (A-1) a glycidyl amine type epoxy resin.

Description

Resin composition {RESIN COMPOSITION}

The present invention is a resin composition containing an epoxy resin and a curing agent; A cured product of the resin composition; A resin sheet comprising the resin composition; A circuit board including the cured product; A semiconductor chip package including the cured product; And a semiconductor device including the semiconductor chip package.

BACKGROUND ART In recent years, demand for small, high-performance electronic devices such as smart phones and tablet-type devices is increasing, and accordingly, an insulating material for semiconductor chip packages used in such small electronic devices is also required to be further enhanced. It is known that such an insulating layer is formed by curing a resin composition (see, for example, Patent Document 1).

Japanese Unexamined Patent Application Publication No. 2017-008312

In particular, in recent years, since a smaller semiconductor chip package is required, an insulating layer and a sealing material used for a semiconductor chip package, and a silicon chip itself are also required to have a thin thickness. For this reason, development of an insulating layer capable of suppressing warpage even if the thickness is thin is required.

However, in thin films, it may be difficult to maintain adhesion strength due to a decrease in the absolute amount of the resin component.In particular, in resin materials used for such applications, adhesion strength against weighting in the vertical direction of the thin film is considered important. have.

An object of the present invention is to provide a resin composition that can suppress the warpage of the resulting cured product and has excellent adhesion to weighting in the vertical direction of the cured product thin film after an environmental test.

In order to achieve the subject of the present invention, the present inventors intensively studied, as a result, by containing (A-1) a glycidylamine-type epoxy resin and (B) a liquid (meth)acrylic polymer at 25°C in the resin composition, It was found that warpage of the cured product can be suppressed, and further, excellent adhesion to weighting in the vertical direction of the cured product thin film after an environmental test is obtained, and the present invention has been completed.

That is, the present invention includes the following contents.

[1] (A) an epoxy resin, (B) a liquid (meth)acrylic polymer at 25°C, (C) a curing agent and (D) an inorganic filler, and the component (A) is (A-1) glycy A resin composition containing a dillamine type epoxy resin.

[2] The resin composition according to [1], wherein the component (A-1) is a bifunctional or trifunctional glycidylamine type epoxy resin.

[3] The above [1] or [2], wherein the content of the component (A-1) is 20% by mass or more and 80% by mass or less when the nonvolatile components other than the (D) component in the resin composition are 100% by mass. The resin composition described in.

[4] Any of the above [1] to [3], wherein the content of the component (B) is 0.5% by mass or more and 20% by mass or less when the nonvolatile components other than the (D) component in the resin composition are 100% by mass. The resin composition according to one.

[5] Any one of [1] to [4], wherein the component (C) is a curing agent selected from the group consisting of a phenolic curing agent, a naphthol curing agent, an acid anhydride curing agent, an amine curing agent and an imidazole curing agent. The resin composition described in.

[6] The resin composition according to any one of [1] to [5], wherein the content of the component (D) is 70% by mass or more when all nonvolatile components in the resin composition are 100% by mass.

[7] The resin composition according to any one of [1] to [6], for forming an insulating layer of a semiconductor chip package.

[8] The resin composition according to any one of [1] to [6], for forming an insulating layer of a circuit board.

[9] The resin composition according to any one of [1] to [6], for sealing a semiconductor chip of a semiconductor chip package.

[10] A cured product of the resin composition according to any one of [1] to [9].

[11] A resin sheet having a support and a resin composition layer comprising the resin composition according to any one of [1] to [9] provided on the support.

[12] A circuit board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [9].

[13] A semiconductor chip package comprising the circuit board according to [12] 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], which seals the semiconductor chip.

[15] A semiconductor device comprising the semiconductor chip package according to [13] or [14].

Advantageous Effects of Invention According to the present invention, a resin composition capable of suppressing warpage of a cured product and excellent in adhesion to weighting in a vertical direction of a cured product thin film after environmental testing; A cured product of the resin composition; A resin sheet comprising the resin composition; A circuit board including the cured product; A semiconductor chip package including the cured product; And a semiconductor device including the semiconductor chip package.

Hereinafter, the present invention will be described in detail based on its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and can be carried out with arbitrary changes within the scope of the claims of the present invention and the scope of their equivalents.

<Resin composition>

The resin composition of the present invention contains (A) an epoxy resin, (B) a liquid (meth)acrylic polymer 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, warpage of the cured product can be suppressed, and excellent adhesion to weighting in the vertical direction of the cured product thin film after an environmental test can be achieved.

The resin composition of the present invention may further contain an optional component in addition to (A) an epoxy resin, (B) a (meth)acrylic polymer in liquid at 25°C, (C) a curing agent, and (D) an inorganic filler. As an arbitrary component, (E) organic solvent and (F) other additives are mentioned, for example. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>

The resin composition of this invention contains (A) epoxy resin.

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

<(A-1) Glycidylamine type epoxy resin>

(A) component contains (A-1) glycidylamine type epoxy resin. (A-1) The glycidylamine type epoxy resin refers to an epoxy resin having at least one glycidylamino group and/or a diglycidylamino group. One epoxy group is included in the glycidylamino group, and two epoxy groups are included in the diglycidylamino group. (A-1) By using a glycidylamine-type epoxy resin, the glass transition temperature (Tg) of the cured product of the resin composition is increased to improve heat resistance, improve the mechanical strength of the cured product, and improve moisture resistance.

(A-1) The glycidylamine type epoxy resin is preferably a bifunctional or higher glycidylamine type epoxy resin having two or more epoxy groups in one molecule from the viewpoint of obtaining a cured product having excellent heat resistance, and one molecule It is more preferable that it is a bifunctional or trifunctional glycidylamine type epoxy resin having 2 or 3 epoxy groups in the resin. Here, the epoxy group is not limited to those derived from a glycidylamino group and a diglycidylamino group, and may also include those derived from a glycidyloxy group. When the nonvolatile component of the glycidylamine type epoxy resin is 100% by mass, the ratio of the bifunctional or more glycidylamine type epoxy resin is from the viewpoint of increasing the heat resistance of the cured product, preferably 50% by mass or more, more It is preferably 60% by mass or more, and 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 the present specification, an aromatic ring refers to an aromatic carbocyclic ring such as a benzene ring and a naphthalene ring, or an aromatic heterocycle such as a pyridine ring, a pyrrole ring, a furan ring, and a thiophene ring. In the case of having two or more aromatic rings in a molecule, the aromatic rings may be directly bonded or bonded via an oxygen atom, an alkylene group, a combination thereof, or the like.

In the present specification, an alkylene group refers to a linear or branched divalent aliphatic saturated hydrocarbon group. An alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 1,1-dimethylethylene group, and the bonding positions thereof are not particularly limited.

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

In the present specification, an alkyl group refers to a linear or branched monovalent saturated aliphatic hydrocarbon group. An alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. As the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1-ethylpropyl And the like.

In this specification, an aryl group refers to a monovalent aromatic hydrocarbon group. An aryl group having 6 to 14 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, biphenylyl group, 2-anthryl group, etc. are mentioned, for example.

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

Examples of the component (A-1) preferable from the viewpoint of remarkably obtaining the desired effect of the present invention include those represented by the following formula (A-1).

[Formula A-1]

In Formula A-1, n each independently represents an integer of 0 to 4. Especially, as for n, the integer of 0-3 is preferable, the integer of 0-2 is more preferable, 0 or 1 is still more preferable, and 1 is especially preferable. In Formula A-1, m represents an integer of 1 to 3. Especially, as for m, 1 or 2 is preferable and 1 is more preferable.

In Formula A-1, each of R ¹¹ independently represents a monovalent epoxy-containing group such as a glycidyloxy group, and a monovalent hydrocarbon group such as an alkyl group and an aryl group. When R ¹¹ is a glycidyloxy group, it is preferable that R ¹¹ is bonded at the para position based on the bonding site of the nitrogen atom and the benzene ring. In addition, when R ¹¹ is an alkyl group, it is preferable that R ¹¹ is bonded to the ortho position based on the bonding site between the nitrogen atom and the benzene ring.

In Formula A-1, R ¹² represents a hydrogen atom or a 1 to trivalent hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group and an arylene group. When m is 1, from the viewpoint of obtaining the desired effect of the present invention, as R ¹² , an alkyl group is preferable and a methyl group is more preferable. Further, when m is 2, from the viewpoint of obtaining the desired effect of the present invention, as R ¹² , an alkylene group is preferable, and a methylene group is more preferable.

In this specification, an arylene group refers to a divalent aromatic hydrocarbon group. An arylene group having 6 to 14 carbon atoms is preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. As an arylene group, a phenylene group, a naphthylene group, a biphenylene group, etc. are mentioned, for example, and their bonding position is not specifically limited.

As specific examples of the component (A-1), ``630'' and ``630LSD'' manufactured by Mitsubishi Chemical (same as the following formula A-2), ``EP-3980S'' manufactured by ADEKA (same as the following formula A-3) ), "EP3950S", "EP3950L", "ELM-100" manufactured by Sumitomo Chemical Co., Ltd., "ELM-100H", "ELM-434", "ELM-434L", and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

[Formula A-2]

[Formula A-3]

(A-1) The epoxy equivalent of the glycidylamine type epoxy resin is preferably 50 to 5,000 g/eq., more preferably 50 to 3,000 g/eq., still more preferably 60 to 2,000 g/eq. ., particularly preferably 70 to 1,000 g/eq. When the epoxy equivalent of the glycidylamine type epoxy resin is in the above range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained.

(A-1) The weight average molecular weight (Mw) of the glycidylamine type epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of a resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

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

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

<Arbitrary epoxy resin other than component (A-1)>

(A) Epoxy resin may further contain other arbitrary epoxy resins in addition to (A-1) glycidylamine type epoxy resin. Other optional epoxy resins include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, tris Phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy 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, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane type epoxy resin, cyclohexane A dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, etc. are mentioned. Other arbitrary epoxy resins may be used alone or in combination of two or more.

It is preferable that the resin composition contains an epoxy resin having two or more epoxy groups per molecule as other optional epoxy resins. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the nonvolatile component of any other epoxy resin is preferably 50% by mass or more, It is more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Epoxy resins include a liquid epoxy resin at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resin”), and a solid epoxy resin at a temperature of 20°C (hereinafter, referred to as “solid epoxy resin”). There is. In one embodiment, a liquid epoxy resin is included as other optional epoxy resins. In one embodiment, a solid epoxy resin is included as other optional epoxy resins. The liquid epoxy resin and the solid epoxy resin may be used in combination.

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

As liquid epoxy resin, 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 novolak type epoxy resin, alicyclic epoxy having an ester skeleton Resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferred.

As a specific example of a liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "EXA-850CRP" manufactured by DIC Corporation, "828US", "828EL" manufactured by Mitsubishi Chemical Corporation, "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin); "JER807" and "1750" manufactured by Mitsubishi Chemical Corporation (bisphenol F type epoxy resin); "JER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" by Shinnittetsu Sumikin Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase Chemtex (glycidyl ester type epoxy resin); "Celoxide 2021P (CEL2021P)" manufactured by Daicel Corporation (alicyclic epoxy resin having an ester skeleton); "PB-3600" by Daicel Corporation, "JP-100" by Nippon Soda Corporation, and "JP-200" (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Shinnittetsu Sumikin Chemical Co., Ltd. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is more preferred.

Examples of the solid epoxy resin include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and Phenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable.

As a specific example of a solid epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; DIC's "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" ( Naphthylene ether type epoxy resin); "EPPN-502H" by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin); "NC7000L" by the Nippon Kayaku company (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Corporation; "ESN475V" manufactured by Shinnittetsu Sumikin Chemical Co., Ltd. (naphthol type epoxy resin); "ESN485" manufactured by Shinnittetsu Sumikin Chemical Co., Ltd. (naphthol novolak type epoxy resin); "YX4000H", "YX4000", and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd. (bixylenol type epoxy resin); "YX8800" manufactured by Mitsubishi Chemical Co., Ltd. (anthracene type epoxy resin); "YX7700" by Mitsubishi Chemical Co., Ltd. (xylene structure-containing novolac type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" by Mitsubishi Chemical Co., Ltd. (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (fluorene type epoxy resin); "JER1010" manufactured by Mitsubishi Chemical (solid bisphenol A type epoxy resin); "JER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as other optional epoxy resins, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin/solid epoxy resin) is preferably 1 or more, more preferably Is 10 or more, particularly preferably 50 or more. When the mass ratio of the liquid epoxy resin and the solid epoxy resin is within this range, the desired effect of the present invention can be remarkably obtained.

The epoxy equivalent of any other epoxy resin is preferably 50 g/eq. To 5,000 g/eq., more preferably 50 g/eq. To 3,000 g/eq., more preferably 80 g/eq. To 2,000 g/eq., even more preferably 110 g/eq. To 1,000 g/eq. By being in such a range, the crosslinking density of the cured product of the resin sheet becomes sufficient, and an insulating layer having a small surface roughness can be formed. Epoxy equivalent is the mass of resin per 1 equivalent of epoxy group. Such an epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of other optional epoxy resins is preferably 100 to 5,000, more preferably 100 to 3,000, still more preferably 100 to 1,500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of a resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

The content of other optional epoxy resins is not particularly limited, but when nonvolatile components other than the component (D) in the resin composition are 100% by mass, preferably 70% by mass or less, more preferably 60% by mass or less, It is more preferably 50% by mass or less, particularly preferably 40% by mass or less. The lower limit is not particularly limited, and can be, for example, 0 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more.

<(B) Liquid (meth)acrylic polymer at 25°C>

The resin composition of the present invention contains (B) a liquid (meth)acrylic polymer at 25°C. Here, the determination of the liquid phase can be performed in accordance with the second "Liquid Confirmation Method" of the Holy Spirit on the test and appearance of dangerous substances (No. In addition, the concept of both an acrylic acid polymer and a methacrylic acid polymer is contained in the term "(meth)acrylic polymer". The terms "(meth)acrylic acid ester" and "(meth)acrylamide" are also the same. The component (B) can exhibit an effect of alleviating stress in the cured product of the resin composition.

The (meth)acrylic polymer refers to a polymer formed by polymerizing a monomer component containing a (meth)acrylic acid ester monomer. In addition to the (meth)acrylic acid ester-based monomer, the (meth)acrylic polymer may contain a (meth)acrylamide-based monomer, a styrene-based monomer, and a functional group-containing monomer as a copolymerization component.

Examples of (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. , T-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, (meth)acrylic acid Aliphatic (meth)acrylic acid esters such as stearyl, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecyl (meth)acrylate; Aromatic (meth)acrylic acid esters such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxypropyl (meth)acrylate; Alkoxy-based (meth)acrylic acid esters such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, and 2-butoxyethyl (meth)acrylate; And halogenated (meth)acrylic acid esters such as chloroethyl (meth)acrylate and trifluoroethyl (meth)acrylate.

Examples of (meth)acrylamide-based monomers include (meth)acrylamide, N-(n-butoxyalkyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-di Ethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and the like. Examples of the styrenic monomer include styrene and α-methylstyrene.

As a functional group-containing monomer, a hydroxy group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a glycidyl group-containing monomer, etc. are mentioned, for example.

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

As a carboxyl group-containing monomer, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, cinnamic acid, etc. are mentioned, for example. As an amino group-containing monomer, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc. are mentioned, for example. As a glycidyl group-containing monomer, glycidyl (meth)acrylate, allyl glycidyl ether, etc. are mentioned, for example.

Moreover, the (meth)acrylic polymer may contain an alkoxysilyl group. Examples of the alkoxysilyl group include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; Dialkoxysilyl groups such as dimethoxymethylsilyl group and diethoxymethylsilyl group; Monoalkoxysilyl groups, such as a methoxydimethylsilyl group and an ethoxydimethylsilyl group, are mentioned. These alkoxysilyl groups may be contained singly or two or more.

As a specific example of the component (B), "ARUFON UP-1000", "ARUFON UP-1010", "ARUFON UP-1020", "ARUFON UP-1021", "ARUFON UP-1061", "ARUFON" manufactured by Toa Kosei Co., Ltd. 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", and "ARUFON US-6170". These may be used individually by 1 type, and may be used in combination of 2 or more types.

The glass transition temperature (Tg) of the component (B) is, for example, 20°C or less, preferably 0°C or less, more preferably -20°C or less, even more preferably -40°C or less, and -50°C The following are particularly preferred.

The weight average molecular weight (Mw) of the component (B) is preferably 100 to 20,000, more preferably 200 to 10,000, still 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 still more preferably 5,000 mPa·s or less. The lower limit is not particularly limited, but may be, for example, 100 mPa·s or more, 200 mPa·s or more, and 300 mPa·s or more.

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

<(C) curing agent>

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

(C) The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include a phenolic curing agent, a naphthol curing agent, an acid anhydride curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate ester. Type curing agent, carbodiimide type curing agent, phosphorus type curing agent, amine type curing agent, imidazole type curing agent, guanidine type curing agent, metal type curing agent, and the like. Curing agents may be used alone or in combination of two or more. The curing agent (C) of the resin composition of the present invention is selected from the group consisting of a phenolic curing agent, a naphthol curing agent, an acid anhydride curing agent, an amine curing agent and an imidazole curing agent from the viewpoint of remarkably obtaining the desired effect of the present invention. It is desirable to be. Moreover, in one embodiment, it is preferable that (C) hardening agent contains an active ester type hardening agent.

As the phenolic curing agent and the naphthol curing agent, from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolac structure or a naphthol curing agent having a novolac structure is preferable. Further, from the viewpoint of adhesion to an adherend, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolac resin is preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenolic curing agent and the naphthol curing agent include, for example, ``MEH-7700'', ``MEH-7810'', ``MEH-7851'', ``MEH-8000H'' manufactured by Maywa Kasei, and manufactured by Nippon Kayaku Corporation. "NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485" manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P" and "LA manufactured by DIC -1356", "TD2090", "TD-2090-60M", etc. are mentioned.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups per molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydro phthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride , Dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromelli anhydride Acid, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3, 3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycolbis (Anhydrotrimellitate), and polymeric acid anhydrides such as styrene maleic resin in which styrene and maleic acid are copolymerized. As commercially available products of the acid anhydride-based curing agent, "HNA-100" and "MH-700" manufactured by Shin-Nippon Rika Co., Ltd. are mentioned.

Although there is no restriction|limiting in particular as an active ester-type hardening agent, In general, 2 ester groups with high reactive activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, per molecule. Compounds having two or more are preferably used. It is preferable that the said active ester hardening agent is obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylate compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. As a phenol compound or a naphthol compound, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolac, and the like. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. An active ester compound is preferable, and among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentaene-phenylene.

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

As specific examples of the benzoxazine-based curing agent, "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Kobunshi Corporation, "P-d", "F-a" manufactured by Shikoku Kasei Kogyo Corporation, etc. are mentioned.

As a cyanate ester curing agent, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6 -Dimethylphenyl cyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4 -Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4- Difunctional cyanate resins such as cyanate phenyl) thioether and bis (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, and some of these cyanate resins are triazineized Prepolymers and the like are mentioned. As specific examples of the cyanate ester curing agent, ``PT30'' and ``PT60'' (both phenol novolak type polyfunctional cyanate ester resins), ``BA230'', ``BA230S75'' (part of bisphenol A dicyanate) manufactured by Ronza Japan Or a prepolymer in which all is triazineized to become a trimer), and the like.

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

Examples of phosphorus-based curing agents include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphos Phonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, and the like.

Examples of the amine curing agent include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabi Cyclo(5,4,0)-undecene, etc., and aliphatic amine curing agents such as 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene; Benzidine, o-triazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane (as a commercial product, ``Kayabond C-100'' manufactured by Nippon Kayaku ), 4,4'-diamino-3,3'-diethylphenylmethane (as a commercial product, "Kayahard AA" manufactured by Nippon Kayaku), 4,4'-diamino-3,3',5,5 '-Tetramethyldiphenylmethane (as a commercial product, "Kayabond C-200S" manufactured by Nippon Kayaku), 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane (as a commercial product, "Kayabond C-300S" manufactured by Nippon Kayaku), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diaminodiphenyl ether , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4 -Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)neopentane, 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline (as a commercial product, Mitsui "Bisaniline M" manufactured by Kagaku), 4,4'-[1,4-phenylenebis(1-methyl-ethylidene)]bisaniline ("bisaniline P" manufactured by Mitsui Chemicals as a commercial product), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (commercially available "BAPP" manufactured by Wakayama Seika), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro And aromatic amine curing agents such as propane and 4,4'-bis(4-aminophenoxy)biphenyl.

Examples of the imidazole-based curing agent include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Midazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimida Sol, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium tri Melitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Midazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tri Azine, 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-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzyl And imidazole compounds such as midazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of an imidazole compound and an epoxy resin.

As the imidazole-based curing agent, a commercial item may be used, and for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation and the like can be mentioned.

As a guanidine-based curing agent, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca. -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. are mentioned.

Examples of the metal-based curing agent include an organic metal complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When a curing agent is included, the amount ratio of the epoxy resin and the curing agent is a ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of reactors of the curing agent], and is preferably in the range of 1:0.2 to 1:2, :0.3 to 1:1.5 are more preferable, and 1:0.4 to 1:1.2 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of curing agent. In addition, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the mass of the nonvolatile component of each epoxy resin by the epoxy equivalent weight for all epoxy resins, and the total number of reactive groups of the curing agent is the nonvolatile component of each curing agent. It is the sum of the value obtained by dividing the mass by the reactor equivalent weight for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent into such a range, the heat resistance of the resulting cured product is further improved.

The content of the component (C) is not particularly limited, but when the nonvolatile components other than the component (D) in the resin composition are 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention, preferably 0.1 It is mass% or more, more preferably 1 mass% or more, still 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, still 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. to be.

<(D) inorganic filler>

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

(D) The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanate, bismuth oxide, titanium oxide , Barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungsten phosphate, and the like, silica and alumina are particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as silica. (D) Inorganic fillers may be used alone or in combination of two or more.

(D) As a commercial item of an inorganic filler, For example, "UFP-30" manufactured by Denka Chemical Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Shinnittetsu Sumikin Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomex Corporation; "UFP-30" manufactured by Denka Corporation; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" and the like manufactured by Adomex Corporation are mentioned.

(D) The average particle diameter of the inorganic filler is not particularly limited, but from the viewpoint of suppressing the generation of flow marks, preferably 40 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less, even more preferably It is preferably 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, still more preferably 3 μm or more, and even more preferably 5 μm or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring device, and making the median diameter the average particle diameter. As a measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone were measured and put in a vial bottle, and the one obtained by dispersing for 10 minutes by ultrasound can be used. Using a laser diffraction type particle diameter distribution measuring apparatus, the measurement sample was made blue and red in wavelength of the light source, and the particle diameter distribution based on the volume of the inorganic filler was measured by a flow cell method, and the median diameter from the obtained particle diameter distribution The average particle diameter was calculated as. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Seisakusho Corporation.

(D) Inorganic fillers are aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable to be treated with one or more surface treatment agents such as. As a commercial item of the surface treatment agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyl trimethoxy Silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by Kogyo Corporation, "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (phenyltrimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Company Limited (long-chain epoxy-type silane couple) Ring agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM503" (3-methacryloxypropyltrimethoxy) Silane), Shin-Etsu Chemical Co., Ltd. "KBM5783", etc. are mentioned.

It is preferable that the degree of surface treatment with the surface treatment agent falls within a predetermined 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% by mass to 5% by mass, preferably surface-treated at 0.2% by mass to 3% by mass, and from 0.3% by mass to It is preferable that the surface treatment is performed at 2% by mass.

The degree of surface treatment with the surface treatment agent can be evaluated according to the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in a sheet form, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

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

(D) The specific surface area of the inorganic filler is preferably 0.01 m 2 /g or more, more preferably 0.1 m 2 /g or more, particularly preferably 0.2 m 2 /g or more from the viewpoint of further improving the effect of the present invention. . Although there is no particular limitation on the upper limit, it is preferably 50 m2/g or less, more preferably 20 m2/g or less, 10 m2/g or less, or 5 m2/g or less. The specific surface area of the inorganic filler is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mauntech Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multi-point method. Lose.

(D) The content of the inorganic filler is not particularly limited, but when all non-volatile components in the resin composition are 100% by mass, from the viewpoint of use in a specific application, preferably 20% by mass or more, more preferably It is 50 mass% or more, more preferably 70 mass% or more, particularly preferably 80 mass% or more. The upper limit is not particularly limited, but can be, for example, 98 mass% or less, 95 mass% or less, 92 mass% or less, 90 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 the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl diglycol acetate, and γ-butyrolactone; Carbitol solvents such as cellosolve and butyl carbitol; Aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene; Amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone; Alcohol solvents such as methanol, ethanol, and 2-methoxypropanol; Hydrocarbon solvents, such as cyclohexane and methylcyclohexane, etc. are mentioned. The organic solvent may be used alone or in combination of two or more in an arbitrary ratio.

In one embodiment, it is preferable that the resin composition of this invention does not contain an organic solvent.

<(F) Other additives>

In addition to the above-described components, the resin composition may further contain other additives as optional components. As such an additive, an organic filler, a thickener, an antifoaming agent, a leveling agent, an adhesive imparting agent, a polymerization initiator, a flame retardant, etc. are mentioned, for example. These additives may be used individually by 1 type, and may be used in combination of 2 or more types. Each content can be appropriately set by those skilled in the art.

<Method of manufacturing resin composition>

In one embodiment, the resin composition of the present invention is, for example, in a reaction container (A) an epoxy resin, (B) a liquid (meth)acrylic polymer at 25°C, (C) a curing agent, (D) an inorganic filler. , If necessary, (E) an organic solvent, and if necessary, (F) other additives, added in an arbitrary order and/or at the same time some or all of them and mixed to prepare a resin composition I can.

In the above process, the temperature in the process of adding each component can be appropriately set, and in the process of adding each component, it may be heated and/or cooled temporarily or over time. You may stir or shake in the process of adding each component. Further, after the above step, it is preferable to further include a step of stirring the resin composition using a stirring device such as a mixer, and dispersing it uniformly.

<Characteristics of resin composition>

The resin composition of the present invention contains (A) an epoxy resin, (B) a liquid (meth)acrylic polymer at 25°C, (C) a curing agent, and (D) an inorganic filler, and the component (A) is (A- 1) Since the glycidylamine-type epoxy resin is included, the cured product can be prevented from warping, and excellent adhesion to the weighting in the vertical direction of the cured product thin film after an environmental test can be obtained. Moreover, in one embodiment, the resin composition of this invention can suppress generation|occurrence|production of a flow mark.

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

In one embodiment, the adhesion strength of the cured product layer (thickness 50 μm; heat cured by heating at 180° C. for 90 minutes) to a silicon wafer after a high temperature and high humidity environmental test (130° C. 85%RH 96 hours) of the resin composition of the present invention is , When the vertical tensile test is performed at 0.1Kg/sec, it is preferably 300Kgf/cm2 or more, more preferably 400Kgf/cm2 or more, still more preferably 450Kgf/cm2 or more, and particularly preferably 500Kgf/cm2 or more.

<Use of resin composition>

The cured product of the resin composition of the present invention is useful for a sealing layer and an insulating layer of a semiconductor due to the above advantages. Therefore, this resin composition can be used as a resin composition for semiconductor sealing or an insulating layer.

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

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

As a semiconductor chip package to which the sealing layer or the 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 Panel Level Package (PLP), and Fan-in type PLP.

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

In addition, the resin composition of the present invention includes a resin composition, such as a resin sheet, sheet-like laminated material such as a prepreg, a liquid material such as resin ink for a solder resist, a die bonding material, a hole filling resin, a component embedding resin, etc. It can be used for a wide range of uses.

<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.

The thickness of the resin composition layer is preferably 600 μm or less, and more preferably 500 μm or less from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer may be preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, still 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, 5 μm or more, more preferably 10 μm or more, still 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, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material includes, for example, polyethylene terephthalate (hereinafter, sometimes abbreviated as ``PET''), polyethylene naphthalate (hereinafter, abbreviated as ``PEN'') There is), etc. polyester; Polycarbonate (hereinafter sometimes abbreviated as "PC"); Acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); Cyclic polyolefin; Triacetylcellulose (hereinafter sometimes abbreviated as "TAC"); Polyether sulfide (hereinafter sometimes abbreviated as "PES"); Polyether ketone; Polyimide, etc. are mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Among them, copper foil is preferred. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good.

The support body may be subjected to treatments such as mat treatment, corona treatment, and antistatic treatment on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. As a releasing agent used for the releasing layer of the support body with a releasing layer, for example, one or more releasing agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins and silicone resins can be mentioned. Examples of commercially available products of the mold release agent include "SK-1", "AL-5", and "AL-7" manufactured by Lintec, which are alkyd resin release agents. Moreover, as a support body with a release layer, it is "Lumira T60" manufactured by Tore, for example; "Purex" manufactured by Teijin; "Uni-Feel" manufactured by the Unityka company, etc. are mentioned.

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

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

Drying may be performed by a known method such as heating and hot air spraying. Drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10 mass% or less, preferably 5 mass% or less. Although it also varies depending on the boiling point of the organic solvent in the resin varnish, for example, in the case of using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, drying the resin at 50°C to 150°C for 3 minutes to 10 minutes A composition layer can be formed.

The resin sheet may contain arbitrary layers other than the support body and the resin composition layer, if necessary. For example, in the resin sheet, a protective film conforming to the support may be provided on a surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent adhesion of dust and the like to the surface of the resin composition layer and scratches. When the resin sheet has a protective film, the resin sheet becomes usable by peeling off the protective film. In addition, the resin sheet can be wound up and stored in a roll shape.

The resin sheet can be suitably used in order to form an insulating layer in the manufacture of a semiconductor chip package (a resin sheet for insulating a semiconductor chip package). For example, a resin sheet can be used to form an insulating layer of a circuit board (a resin sheet for an insulating layer of a circuit board). Examples of packages using such substrates include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

In addition, a resin sheet can be suitably used in order to seal a semiconductor chip (resin sheet for semiconductor chip sealing). Examples of applicable semiconductor chip packages include fan-out type WLP, fan-in type WLP, fan-out type PLP, and fan-in type PLP.

Further, the resin sheet may be used as a material for the MUF used after the semiconductor chip is connected to the substrate.

Additionally, the resin sheet can be used for a wide range of other applications requiring high insulation reliability. For example, a resin sheet can be suitably used in order to form 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 from a cured product of the resin composition of the present invention. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).

(1) A step of forming a resin composition layer on a substrate.

(2) A step of thermosetting the resin composition layer to form an insulating layer.

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

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

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

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

The conductor layer is, for example, a step of laminating a dry film (photosensitive resist film) on a substrate, and a step of forming a pattern by forming a pattern by exposing and developing the dry film under predetermined conditions using a photomask. , Forming a conductor layer by a plating method such as an electrolytic plating method using the developed pattern dry film as a plating mask, and a method including a step of peeling the pattern dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, and for example, a dry film made of a resin such as novolac resin or acrylic resin can be used. The lamination conditions of the substrate and the dry film may be the same as the lamination conditions of the substrate and the resin sheet described later. Peeling of the dry film can be performed using, for example, an alkaline peeling solution such as sodium hydroxide solution.

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

The formation of the resin composition layer is performed, for example, by laminating a resin sheet and a substrate. Such lamination can be performed, for example, by bonding a resin composition layer to the substrate by heat-press bonding the resin sheet to the substrate from the support side. As a member for heat-pressing the resin sheet to the substrate (hereinafter, sometimes referred to as ``heat-pressing member''), for example, a heated metal plate (SUS hard plate, etc.) or a metal roll (SUS roll, etc.) may be mentioned. . In addition, it is preferable not to press the heat-compressed member directly onto the resin sheet, but to press the heat-resistant rubber or the like between the elastic material so that the resin sheet sufficiently follows the surface irregularities of the base material.

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

After lamination, the laminated resin sheet may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the heat-pressed member from the support side. The press conditions of the smoothing treatment can be set to the same conditions as the heat-pressing conditions of the lamination. In addition, lamination and smoothing treatment may be performed continuously using a vacuum laminator.

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

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

Before thermosetting the resin composition layer, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, at a temperature of usually 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less), the resin composition layer You may pre-heat for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) normally.

In the manner described above, a circuit board having an insulating layer can be manufactured. Further, the circuit board manufacturing method may further include an arbitrary step.

For example, when a circuit board is manufactured using a resin sheet, the manufacturing method of the circuit board may include a step of peeling the support of the resin sheet. The support may be peeled off before thermal curing of the resin composition layer, or may be peeled off after thermal curing of the resin composition layer.

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

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

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

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

After the via hole is formed, a conductor layer may be formed on the insulating layer. By forming the conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the substrate communicate with each other, and interlayer connection is performed. Examples of the method for forming the conductor layer include a plating method, a sputtering method, and a vapor deposition method, and among them, a plating method is preferable. In a preferred embodiment, a conductive layer having a desired wiring pattern is formed by plating the surface of the insulating layer by a suitable method such as a semi-positive method and a full-positive method. In addition, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by the subtractive method. The material of the formed conductor layer may be a single metal or an alloy. Further, this conductor layer may have a single-layer structure, or may have 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 the insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer is formed corresponding to a desired wiring pattern. After the electroplating layer is formed by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by a process such as etching, so that a conductor layer having a desired wiring pattern can be formed. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as the said dry film.

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

<Semiconductor Chip Package>

A semiconductor chip package according to a first embodiment of the present invention includes the 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 board.

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

As an example of a bonding method, a method of compressing a semiconductor chip to a circuit board is mentioned. 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, more preferably in the range of 140°C to 180°C), and the pressing time is usually between 1 second and 60 seconds. Range (preferably from 5 seconds to 30 seconds).

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

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

A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition for sealing the semiconductor chip. In such a semiconductor chip package, usually, the cured product of the resin composition functions as a sealing layer. As the semiconductor chip package according to the second embodiment, a fan-out type WLP is exemplified.

The manufacturing method of such a semiconductor chip package,

(A) the step of laminating a temporary fixing film on the substrate,

(B) the process of temporarily fixing the semiconductor chip on the temporary fixing film,

(C) the step of forming a sealing layer on the semiconductor chip,

(D) the step of peeling the substrate and the temporary fixing film from the semiconductor chip,

(E) a step of forming a rewiring forming layer as an insulating layer on the surface from which the substrate and the temporary fixing film of the semiconductor chip are peeled off,

(F) a step of forming a redistribution layer as a conductor layer on the redistribution formation layer, and

(G) A step of forming a solder resist layer on the redistribution layer is included. In addition, the method of manufacturing the semiconductor chip package,

(H) The process of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and subdividing them may be included.

(Step (A))

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

Examples of the substrate include silicon wafers; Glass wafer; Glass substrate; Metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheet (SPCC); Substrates, such as FR-4 substrates, in which glass fibers are wetted with an epoxy resin or the like and subjected to a thermosetting treatment; And a substrate made of a bismaleimide triazine resin such as BT resin.

The temporary fixing film can be peeled off from the semiconductor chip, and any material capable of temporarily fixing the semiconductor chip can be used. As a commercial item, "Revalpha" by Nitto Denko Corporation etc. is mentioned.

(Step (B))

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

(Step (C))

Step (C) is a step of forming a sealing layer on a semiconductor chip. The sealing layer is formed by the cured product of the aforementioned resin composition. The sealing layer is usually formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of thermosetting the resin composition layer to form a sealing layer.

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

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

In addition, a specific operation of the compression molding method may be performed as follows, for example. As a compression molding mold, an upper mold and a lower mold are prepared. The resin composition is put on the lower mold. Further, a semiconductor chip is attached to the upper mold together with the substrate and the temporary fixing film. Thereafter, the upper mold and the lower mold are mold-fastened so that the resin composition placed on the lower mold comes into contact with the semiconductor chip attached to the upper mold, and compression molding is performed by applying heat and pressure.

Molding conditions vary depending on the composition of the resin composition, and appropriate conditions can be adopted so that good sealing is achieved. For example, the temperature of the mold during molding is preferably a temperature at which the resin composition can exhibit excellent compression moldability, preferably 80°C or higher, more preferably 100°C or higher, and particularly preferably 120°C or higher. , Preferably 200°C or less, more preferably 170°C or less, and particularly preferably 150°C or less. In addition, the pressure applied at the time of 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 cure 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. to be. Usually, after formation of the resin composition layer, the mold is separated. Separation of the mold may be performed before thermosetting of the resin composition layer or after thermosetting.

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

After forming the resin composition layer on the semiconductor chip, the resin composition layer is thermosetted to obtain a sealing layer covering the semiconductor chip. Thereby, sealing of the semiconductor chip with the cured product of the resin composition is performed. As the thermosetting conditions of the resin composition layer, the same conditions as the thermosetting conditions of the resin composition layer in the circuit board manufacturing method may be adopted. Further, before thermosetting the resin composition layer, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. As the processing conditions for such preliminary heat treatment, the same conditions as the preliminary heat treatment in the circuit board manufacturing method may be adopted.

(Step (D))

Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. As for the peeling method, it is preferable to adopt an appropriate method according to the material of the temporary fixing film. As a peeling method, a method of peeling by heating, foaming, or expanding a temporary fixing film is mentioned, for example. In addition, as a peeling method, for example, a method of irradiating the temporary fix film with ultraviolet rays through a base material, reducing the adhesive force of a temporary fix film, and peeling is mentioned.

In the method of peeling by heating, foaming, or expanding the temporary fixing film, the heating conditions are usually at 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method of peeling off by irradiating with ultraviolet rays to lower the adhesive force of the temporary fixing film, the irradiation amount of ultraviolet rays is usually 10 mJ/cm 2 to 1,000 mJ/cm 2.

(Step (E))

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

Any material having insulating properties can be used as the material for the rewiring forming layer. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of easiness of manufacturing a semiconductor chip package. Further, as such a thermosetting resin, the resin composition of the present invention may be used.

After the redistribution formation layer is formed, a via hole may be formed in the redistribution formation layer in order to connect the semiconductor chip and the redistribution layer between layers.

In the method of forming a via hole when the material of the redistribution forming layer is a photosensitive resin, the surface of the redistribution forming layer is usually irradiated with active energy rays through a mask pattern to photo-cure the redistribution forming layer of the irradiation part. Examples of the active energy ray include ultraviolet rays, visible rays, electron rays, X rays, and the like, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. Examples of the exposure method include a contact exposure method in which a mask pattern is in close contact with the redistribution forming layer to expose the light, and a non-contact exposure method in which the mask pattern is exposed using parallel light rays without intimate contact with the redistribution forming layer.

After photocuring the redistribution forming layer, the redistribution forming layer is developed, the unexposed portion is removed, and a via hole is formed. Development may be performed either wet development or dry development. As a method of development, a dip method, a paddle method, a spray method, a brushing method, a scraping method, etc. can be mentioned, for example, and a paddle method is suitable from the viewpoint of resolution.

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

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

(Step (F))

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

(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, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of easiness of manufacturing a semiconductor chip package. Moreover, as a thermosetting resin, you may use the resin composition of this invention.

In addition, in step (G), bumping processing for forming bumps may be performed as necessary. The bumping process can be performed by a method such as solder ball or solder plating. In addition, formation of the via hole in the bumping process can be performed in the same manner as in the step (E).

(Step (H))

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

<Semiconductor device>

A semiconductor device includes a semiconductor chip package. As a semiconductor device, for example, electrical appliances (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (e.g., motorcycles, And various semiconductor devices provided in automobiles, tanks, ships, aircraft, etc.).

[Example]

Hereinafter, the present invention will be described in detail by examples. The present invention is not limited to these examples. In addition, in the following, "parts" and "%" indicating amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Example 1>

2 parts of glycidylamine-type epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115g/eq.), glycidylamine-type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, 95g/eq. of epoxy equivalent) 3 parts, liquid acrylic polymer ("UP-1020" manufactured by Toa Gosei, viscosity (25°C) 500mPa·s, Mw 2,000, Tg -80°C) 1 part, bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC) ", epoxy equivalent 170 to 175 g/eq.) 6 parts, acid anhydride curing agent ("HNA-100" manufactured by Shin Nippon Rica, acid anhydride equivalent 179 g/eq.) 6 parts, silica A 83 parts, imidazole-based curing agent ( Shikoku Kasei Co., Ltd. "2E4MZ", 2-ethyl-4-methylimidazole) 0.1 part was uniformly dispersed using a mixer to prepare a resin composition.

<Example 2>

Instead of 1 part of liquid acrylic polymer ("UP-1020" manufactured by Toa Kosei, Inc.), liquid acrylic polymer ("UG-4010" manufactured by Toa Kosei, Inc., viscosity (25°C) 3,700 mPa·s, Mw 2,900, Tg -57°C ) Except having used 1 part, it carried out similarly to Embodiment 1, and prepared the resin composition.

<Example 3>

Instead of 1 part of liquid acrylic polymer ("UP-1020" manufactured by Toa Kosei), liquid acrylic polymer ("US-6100" manufactured by Toa Kosei, viscosity (25°C) 2,300 mPa·s, Mw 2,500, Tg -58°C) ) Except having used 1 part, it carried out similarly to Example 1, and prepared the resin composition.

<Example 4>

Glycidylamine type epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115g/eq.) 1 part, glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, epoxy equivalent 95g/eq.) 10 parts, liquid acrylic polymer ("UP-1020" manufactured by Toa Gosei, viscosity (25°C) 500mPa·s, Mw 2,000, Tg -80°C) 1 part, bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC) '', epoxy equivalent 170 to 175 g/eq.) 6 parts, phenolic curing agent (Meiwa Kasei ``MEH-8000H'') 1 part, silica A 83 parts, imidazole curing agent (Shikoku Kasei Kasei ``2E4MZ'', 2 -Ethyl-4-methylimidazole) 0.4 part was uniformly dispersed using a mixer to prepare a resin composition.

<Example 5>

In the same manner as in Example 4, a resin composition was prepared in the same manner as in Example 4, except that 1 part of the amine-based curing agent (``KAYABOND C-200S'' manufactured by Nippon Kayaku Corporation) was used instead of 1 part of the phenolic curing agent (Meiwa Kasei) Prepared.

<Example 6>

A resin composition was prepared in the same manner as in Example 1 except that 95 parts of alumina A was used instead of 83 parts of silica A.

<Example 7>

The amount of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, 95 g/eq. of epoxy equivalent) was increased to 3.5 parts, and the amount of liquid acrylic polymer ("UP-1020" manufactured by Toa Kosei) was increased to 0.5 part. Except having reduced the weight, it carried out similarly to Example 1, and prepared the resin composition.

<Example 8>

Glycidylamine type epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115g/eq.) 4 parts, glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, epoxy equivalent 95g/eq.) 9 parts, liquid acrylic polymer ("UP-1020" manufactured by Toa Kosei, viscosity (25°C) 500mPa·s, Mw 2,000, Tg -80°C) 1 part, acid anhydride curing agent ("HNA-100" manufactured by Shin-Nippon Rica) '', acid anhydride equivalent 179 g/eq.) 4 parts, silica A 83 parts, imidazole-based curing agent ("2E4MZ", 2-ethyl-4-methylimidazole manufactured by Shikoku Kasei Co., Ltd.)0.1 parts uniformly using a mixer It dispersed and prepared a resin composition.

<Example 9>

Glycidylamine type epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115g/eq.) 1 part, glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical, epoxy equivalent 95g/eq.) 1 part, liquid acrylic polymer ("UP-1020" manufactured by Toa Gosei, viscosity (25°C) 500mPa·s, Mw 2,000, Tg -80°C) 1 part, bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC) ", epoxy equivalent 170 to 175 g/eq.) 9 parts, acid anhydride curing agent ("HNA-100" manufactured by Shin Nippon Rica, acid anhydride equivalent 179 g/eq.) 6 parts, silica A 83 parts, imidazole-based curing agent ( Shikoku Kasei Co., Ltd. "2E4MZ", 2-ethyl-4-methylimidazole) 0.1 part was uniformly dispersed using a mixer to prepare a resin composition.

<Example 10>

The amount of bisphenol A epoxy resin ("EXA-850CRP" manufactured by DIC, epoxy equivalent 170 to 175 g/eq.) was reduced to 2 parts, and the amount of liquid acrylic polymer ("UP-1020" manufactured by Toa Kosei) was reduced to 5 Except having increased by part, it carried out similarly to Example 1, and prepared the resin composition.

<Comparative Example 1>

A resin composition was prepared in the same manner as in Example 1 except that the acrylic polymer ("UP-1020" manufactured by Toa Kosei Co., Ltd.) was not used.

<Used inorganic filler>

Silica A: spherical silica treated with an average particle diameter of 6.0 μm, a maximum cut diameter of 20 μm, a specific surface area of 4.8 m 2 /g, and KBM573 (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.).

Alumina A: spherical alumina treated with an average particle diameter of 4.8 μm, a maximum cut diameter of 24 μm, a specific surface area of 2.7 m 2 /g, and KBM573 (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.).

<Test Example 1: Evaluation of warpage>

On a 12-inch silicon wafer, the resin composition prepared in Examples and Comparative Examples was compression molded using a compression mold apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes), and a resin composition layer having a thickness of 300 μm Formed. Then, it heated at 180 degreeC for 90 minutes, and the resin composition layer was thermosetted. Thereby, a sample substrate including a silicon wafer and a cured product layer of a resin composition was obtained. Using a shadow moire measuring device ("ThermoireAXP" manufactured by Akorometrix), the amount of warpage of the sample substrate at 25°C was measured. The measurement was performed in accordance with JEITA EDX-7311-24 of the Electronic Information Technology Industry Association standard. Specifically, the virtual plane calculated by the least squares method of all data on the substrate surface of the measurement region was used as the reference plane, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane was determined as the amount of warpage. The amount of warpage was evaluated as "○" for less than 2 mm, 2 mm or more, and "△" for less than 3 mm, and "x" for 3 mm or more.

<Test Example 2: Evaluation of appearance>

The appearance of the resin layer of the sample substrate prepared in Test Example 1 was observed. Among the entire surface of the resin layer, a flow mark having an area occupied by less than 20% was designated as "○", and an area exceeding 20% was designated as "△".

<Test Example 3: Adhesion evaluation after high temperature high humidity environmental test (HAST)>

Using the sample substrate prepared in Test Example 1, a high-temperature, high-humidity environmental test (HAST) was conducted under conditions of 130°C and 85%RH for 96 hours. The cured product after HAST implementation was polished using #180 sandpaper until the resin layer became 50 µm thick. The polished sample was cut into a 1 cm wide test piece, and a φ2.7 mm adhesive stud pin was placed vertically with respect to the resin layer, heated at 150°C for 60 minutes, and the test piece to which the stud pin and the resin layer were adhered. I wrote. The obtained test piece with stud pin was measured in a vertical tensile test at a test speed of 0.1 Kg/sec using a vertical tensile tester ROMULUS manufactured by QUAD GROUP. Measurements were performed on five test pieces, and an average value was calculated. The adhesive strength exceeding 500 Kgf/cm 2 was defined as "○", and the adhesive strength of less than 500 Kgf/cm 2 was defined as "X".

Table 1 shows the nonvolatile components of the resin compositions of Examples and Comparative Examples, their usage, and evaluation results of the test examples.

From the above results, when (A-1) a glycidylamine type epoxy resin and (B) a liquid (meth)acrylic polymer at 25°C are used, the cured product can be prevented from warping, and the cured product after the environmental test It has been found that excellent adhesion to the weighting in the vertical direction of the thin film can be achieved.

Claims (16)

(A) epoxy resin, (B) liquid (meth)acrylic polymer at 25°C, (C) curing agent and (D) inorganic filler, and component (A) is (A-1) glycidylamine type A resin composition containing an epoxy resin. The resin composition according to claim 1, wherein the component (A-1) is a bifunctional or trifunctional glycidylamine type epoxy resin. The resin composition according to claim 1, wherein the content of the component (A-1) is 20% by mass or more and 80% by mass or less when the nonvolatile components other than the (D) component in the resin composition are 100% by mass. The resin composition according to claim 1, wherein the content of the component (B) is 0.5% by mass or more and 20% by mass or less when the nonvolatile components other than the (D) component in the resin composition are 100% by mass. The resin composition according to claim 1, wherein the component (C) is a curing agent selected from the group consisting of a phenol curing agent, a naphthol curing agent, an acid anhydride curing agent, an amine curing agent, and an imidazole curing agent. The resin composition according to claim 1, wherein the content of the component (D) is 70 mass% or more when all nonvolatile components in the resin composition are 100 mass%. The resin composition according to claim 1, for forming an insulating layer of a semiconductor chip package. The resin composition according to claim 1, for forming an insulating layer of a circuit board. The resin composition according to claim 1, for sealing a semiconductor chip of a semiconductor chip package. A cured product of the resin composition according to any one of claims 1 to 9. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 9 provided on the support. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor chip package comprising the circuit board according to claim 12 and a semiconductor chip mounted on the circuit board. A semiconductor device comprising 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 comprising the semiconductor chip package according to claim 15.