Resin composition

Abstract

An object of the present invention is to provide a resin composition capable of obtaining a cured product having excellent adhesion to a conductor layer even after a HAST test; a circuit board and a semiconductor chip package using the resin composition. A solution of the present invention is a resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the amount of chloride ions contained in the resin composition, as measured by combustion-ion chromatography (BS EN 14582 2007), is 50 ppm or less.

Description

Technical Field

[0001] The present invention relates to a resin composition. Further, the present invention relates to a circuit board and a semiconductor chip package using the resin composition. Background Art

[0002] In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased. Along with this, there has been a pursuit of higher functionality for insulating materials that can be used as sealing layers or insulating layers for these small electronic devices. As such an insulating material, for example, a material formed by curing a resin composition is known (see, for example, Patent Documents 1 and 2).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2013 - 237715

[0006] Patent Document 2: Japanese Patent No. 6288344. Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] The present inventors have studied a resin composition that can form a sealing layer or an insulating layer, and as a result, have found that by containing an inorganic filler in the resin composition, the coefficient of thermal expansion (Coefficient of Thermal Expansion, sometimes referred to as "CTE") can generally be reduced, but when performing an environmental test (HAST test) in a high-temperature and high-humidity environment, the adhesion between the insulating layer and a conductor layer such as a copper foil decreases.

[0009] The present invention is an original invention in view of the above problems, and an object thereof is to provide: a resin composition that can obtain a cured product having excellent adhesion to a conductor layer even after a HAST test; a circuit board using the resin composition; and a semiconductor chip package.

[0010] Means for Solving the Problems

[0011] The present inventors have made diligent studies to solve the above problems, and as a result, have found that by making the amount of chloride ions contained in the resin composition be below a certain value, a cured product having excellent adhesion to a conductor layer even after a HAST test can be obtained, thereby completing the present invention.

[0012] That is, the present invention includes the following content,

[0013] [1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler.

[0014] Among them, the amount of chloride ions contained in the resin composition, measured by the sample combustion-ion chromatography method (BS EN 14582 2007), is 50 ppm or less;

[0015] [2] The resin composition according to [1], wherein when the non-volatile components in the resin composition are set to 100% by mass, the content of component (C) is 80% by mass or more;

[0016] [3] The resin composition according to [1] or [2], wherein the coefficient of thermal expansion of the cured product obtained by thermally curing the resin composition at 180 °C for 90 minutes is 15 ppm or less;

[0017] [4] The resin composition according to any one of [1] to [3], wherein component (B) contains an acid anhydride-based curing agent;

[0018] [5] The resin composition according to any one of [1] to [4], wherein the resin composition is in a liquid state;

[0019] [6] The resin composition according to any one of [1] to [5], which is a resin composition for sealing or for an insulating layer;

[0020] [7] A circuit board, which includes an insulating layer formed by using the cured product of the resin composition according to any one of [1] to [6];

[0021] [8] A semiconductor chip package, which includes the circuit board according to [7] and a semiconductor chip mounted on the circuit board;

[0022] [9] A semiconductor chip package, which includes a semiconductor chip and the cured product of the resin composition according to any one of [1] to [6] that seals the semiconductor chip.

[0023] Effects of the Invention

[0024] According to the present invention, it is possible to provide a resin composition capable of obtaining a cured product having excellent adhesion to a conductor layer even after a HAST test; a circuit board and a semiconductor chip package using the resin composition. Detailed Description of the Invention

[0025] Hereinafter, embodiments and examples are shown to describe the present invention in detail. However, the present invention is not limited to the embodiments and examples listed below, and can be arbitrarily changed and implemented within the scope not departing from the claims of the present invention and their equivalent scope. In addition, "ppm" is based on mass unless otherwise specified.

[0026] [Resin Composition]

[0027] The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler. Among them, the amount of chloride ions contained in the resin composition, as measured by the sample combustion - ion chromatography method (BS EN 14582 2007), is 50 ppm or less. By making the amount of chloride ions contained in the resin composition 50 ppm or less, a cured product having excellent adhesion to a conductor layer such as a copper foil even after the HAST test can be obtained.

[0028] As described above, by containing a relatively large amount of an inorganic filler in the resin composition, the coefficient of thermal expansion can be reduced, but the adhesion to the conductor layer after the HAST test decreases.

[0029] However, as a result of the intensive research by the present inventors, by making the amount of chloride ions contained in the resin composition 50 ppm or less, the adhesion to the conductor layer after the HAST test can be improved.

[0030] The present inventors speculate as follows: By making the amount of chloride ions contained in the resin composition 50 ppm or less, a configuration having the excellent advantages as described above can be obtained. However, the technical scope of the present invention is not limited by the configuration described below. Epichlorohydrin may be contained as an impurity in the component (A). By removing this epichlorohydrin, corrosion of the conductor layer such as a copper foil by the chloride ions of epichlorohydrin can be suppressed. As a result, a cured product having excellent adhesion to the conductor layer even after the HAST test can be obtained. Therefore, the present invention is excellent in that even when a relatively large amount of an inorganic filler is contained in the resin composition, both the reduction of the coefficient of thermal expansion and the improvement of the adhesion to the conductor layer after the HAST test can be achieved.

[0031] In addition, in the resin composition, in addition to containing the components (A) to (C), any arbitrary components may be further contained. Examples of the arbitrary components include (D) a curing accelerator and (E) other additives. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

[0032] <(A) Epoxy resin>

[0033] The resin composition contains (A) an epoxy resin as component (A). Examples of the (A) epoxy resin 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, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic type epoxy resin, epoxy resin containing a spiro ring, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. The epoxy resin may be used alone or in combination of two or more.

[0034] In the resin composition, it is preferable to contain, as the (A) epoxy resin, an epoxy resin having 2 or more epoxy groups in 1 molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on 100% by mass of the non-volatile components of the (A) epoxy resin.

[0035] The epoxy resin includes an epoxy resin that is liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). In the resin composition, as the (A) epoxy resin, the liquid epoxy resin can be used, the solid epoxy resin can be used, or the liquid epoxy resin and the solid epoxy resin can be used in combination. Among them, from the viewpoint of reducing the viscosity of the resin composition, it is preferable to use the liquid epoxy resin.

[0036] As the liquid epoxy resin, it is preferable to use a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

[0037] As the liquid epoxy resin, it is preferably a bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin such as an alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure, and more preferably glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin.

[0038] As specific examples of the liquid epoxy resin, the following can be cited: "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", "EPIKOTE 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase Chemtex Corporation; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EP3950L" (glycidylamine-type epoxy resin) manufactured by ADEKA Corporation, etc. These can be used alone or in combination of two or more.

[0039] As the solid epoxy resin, it is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule.

[0040] As the solid epoxy resin, it is preferably xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylidene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, tetraphenylethane-type epoxy resin, and more preferably bisphenol AF-type epoxy resin, biphenyl-type epoxy resin, xylenol-type epoxy resin.

[0041] As specific examples of the solid epoxy resin, the following can be cited: "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700", "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; "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "ESN485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (xylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used alone or in combination of two or more.

[0042] However, the epoxy resins of the above-mentioned commercial products may contain epichlorohydrin. Therefore, for the epoxy resins of commercial products, they are usually used after a purification treatment for removing epichlorohydrin. Thereby, the amount of chloride ions in the resin composition can be reduced. As the purification treatment, distillation etc. can be cited for example.

[0043] As for (A) epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, their quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10 in terms of mass ratio. By setting the quantitative ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the effects desired by the present invention can be significantly obtained. Further, when it is usually used in the form of a resin sheet, appropriate adhesiveness can be brought about. In addition, when it is usually used in the form of a resin sheet, sufficient flexibility can be obtained, and the workability is improved. Further, a cured product having sufficient breaking strength can usually be obtained.

[0044] The epoxy equivalent of (A) epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., still more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By being within this range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with a small surface roughness can be brought about. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0045] From the viewpoint of significantly obtaining the effects desired by the present invention, the weight average molecular weight (Mw) of (A) epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) method as a value in terms of polystyrene conversion.

[0046] From the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, when the non-volatile components in the resin composition are set to 100% by mass, the content of (A) epoxy resin is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. From the viewpoint of significantly obtaining the effects desired by the present invention, the upper limit of the content of the epoxy resin is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. It should be noted that in the present invention, the content of each component in the resin composition is the value when the non-volatile components in the resin composition are set to 100% by mass unless otherwise specified.

[0047] From the viewpoint of making the amount of chloride ions in the resin composition 50 ppm or less, usually, it is preferably to distill (A) epoxy resin before preparing the resin composition to remove epichlorohydrin which is the main component of impurities in (A) epoxy resin. The distillation temperature of (A) epoxy resin, the pressure during distillation, etc. can be appropriately changed according to the type of (A) epoxy resin.

[0048] <(B) Curing Agent>

[0049] The resin composition contains (B) a curing agent as component (B). The (B) curing agent generally has the function of reacting with component (A) to cure the resin composition. One kind of (B) curing agent can be used alone, or two or more kinds can be used in combination.

[0050] Examples of the (B) curing agent include, for example, acid anhydride-based curing agents, active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, amine-based curing agents, etc. Among them, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably to contain an acid anhydride-based curing agent.

[0051] Examples of the acid anhydride-based curing agent include curing agents having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitate), polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid, etc.

[0052] Examples of commercially available acid anhydride-based curing agents include "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

[0053] As the active ester-based curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester-based curing agent, it is preferably a compound having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. The active ester-based curing agent is preferably a compound obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferably an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound, and more preferably an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound.

[0054] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like.

[0055] Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene type diphenol compound, phenol novolac, and the like. Herein, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.

[0056] Preferable specific examples of the active ester type curing agent include: an active ester type curing agent containing a dicyclopentadiene type diphenol structure, an active ester type curing agent containing a naphthalene structure, an active ester type curing agent containing an acetylated product of phenol novolac, and an active ester type curing agent containing a benzoylated product of phenol novolac. Among them, more preferable are an active ester type curing agent containing a naphthalene structure and an active ester type curing agent containing a dicyclopentadiene type diphenol structure. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit formed by phenylene-dicyclopentylene-phenylene.

[0057] Examples of the commercially available products of the active ester type curing agent include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "HPC-8000H-65TM", "HPC-8150-62T", "EXB-8000L-65TM" (manufactured by DIC Corporation), etc. for the active ester type curing agent containing a dicyclopentadiene type diphenol structure; "EXB-8100L-65T", "EXB-8150L-65T", "EXB9416-70BK", "EXB-8150-65T" (manufactured by DIC Corporation), etc. for the active ester type curing agent containing a naphthalene structure; "DC808" (manufactured by Mitsubishi Chemical Corporation), etc. for the active ester type curing agent containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), etc. for the active ester type curing agent containing a benzoylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc. for the active ester type curing agent containing a benzoylated product of phenol novolac.

[0058] As a phenol-based curing agent and a naphthol-based curing agent, from the viewpoints of heat resistance and water resistance, a curing agent having a novolac structure is preferably used. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferably used, and a phenol-based curing agent having a triazine skeleton is more preferably used.

[0059] Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwafosis Co., Ltd.; "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. manufactured by DIC Corporation.

[0060] Specific examples of the benzoxazine-based curing agent include "JBZ-OD100" (benzoxazine ring equivalent: 218), "JBZ-OP100D" (benzoxazine ring equivalent: 218), "ODA-BOZ" (benzoxazine ring equivalent: 218) manufactured by JFE Chemical Corporation; "P-d" (benzoxazine ring equivalent: 217), "F-a" (benzoxazine ring equivalent: 217) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "HFB2006M" (benzoxazine ring equivalent: 432) manufactured by Showa Highpolymer Co., Ltd.

[0061] Examples of the cyanate ester curing agent include difunctional cyanate ester resins such as bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylidene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanatophenyl)propane, 1,1-bis(4-cyanatophenyl)methane, bis(4-cyanatophenyl-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl) sulfide, and bis(4-cyanatophenyl) ether; polyfunctional cyanate ester resins derived from phenol novolac and cresol novolac; prepolymers obtained by triazine-forming a part of these cyanate ester resins. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymers in which a part or all of bisphenol A dicyanate is triazine-formed to form a trimer) manufactured by Lonza Japan Co., Ltd.

[0062] Specific examples of the carbodiimide curing agent include CARBODILITE (registered trademark) V-03 (carbodiimide equivalent: 216), V-05 (carbodiimide equivalent: 262), V-07 (carbodiimide equivalent: 200); V-09 (carbodiimide equivalent: 200) manufactured by Nisshinbo Chemical Inc.; and Stabaxol (registered trademark) P (carbodiimide equivalent: 302) manufactured by Rhein Chemie.

[0063] As the amine-based curing agent, curing agents having one or more amino groups in one molecule can be cited, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, from the viewpoint of achieving the effects expected by the present invention, aromatic amines are preferably used. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenylsulfone diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. The amine-based curing agent can be a commercially available product, and examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., and "EPICURE W" manufactured by Mitsubishi Chemical Corporation, etc.

[0064] (A) The amount ratio of the epoxy resin to (B) the curing agent is preferably in the range of 1:0.01 to 1:10, more preferably 1:0.1 to 1:5, and even more preferably 1:1 to 1:3 in terms of the ratio of [total number of epoxy groups of the epoxy resin]:[total number of reactive groups of the curing agent]. Here, the reactive group of the curing agent is an active hydroxyl group, etc., and it varies depending on the type of the curing agent. In addition, the total number of epoxy groups of the epoxy resin refers to the value obtained by summing up the values obtained by dividing the solid component mass of each epoxy resin by the epoxy equivalent for all the epoxy resins, and the total number of reactive groups of the curing agent refers to the value obtained by summing up the values obtained by dividing the solid component mass of each curing agent by the reactive group equivalent for all the curing agents. By setting the amount ratio of the epoxy resin to the curing agent within the above range, the heat resistance of the cured product of the resin composition is further improved.

[0065] From the viewpoint of significantly obtaining the desired effects of the present invention, the content of the (B) curing agent is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0066] <(C) Inorganic filler>

[0067] The resin composition contains (C) an inorganic filler as the (C) component. By using the (C) inorganic filler, the linear thermal expansion coefficient of the cured product of the resin composition can be reduced.

[0068] As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include 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, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among them, calcium carbonate and silica are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. In addition, as silica, spherical silica is preferably used. The (C) inorganic filler can be used alone or in combination of two or more.

[0069] Examples of commercially available products as the (C) component include "ST7030-20" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "MSS-6", "AC-5V" manufactured by Ryosen Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30", "SFP-130MC", "FB-7SDC", "FB-5SDC", "FB-3SDC" manufactured by Denka Company Limited; "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "FE9" manufactured by Admatechs Co., Ltd., etc.

[0070] The specific surface area of the (C) component is preferably 1 m 2 / g or more, more preferably 2 m2 above / g, preferably 3 m 2 above / g. There is no particular limitation on the upper limit, preferably 60 m 2 below / g, 50 m 2 below / g or 40 m 2 below / g. The specific surface area can be obtained by adsorbing nitrogen on the surface of the sample using a BET full-automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area by the BET multi-point method.

[0071] From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle diameter of the component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less.

[0072] (C) The average particle diameter of the component can be measured by the laser diffraction-scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the median particle size thereof can be used as the average particle diameter for measurement. As the measurement sample, a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a test tube and dispersing them ultrasonically for 10 minutes can be used. For the measurement sample, using a laser diffraction type particle size distribution measuring device, the light source wavelength used is set to blue and red, and the volume-based particle size distribution of the component (C) is measured in a flow cell manner, and the average particle diameter is calculated as the median particle size from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0073] From the viewpoints of improving moisture resistance and dispersibility, the component (C) is preferably treated with a surface treatment agent. Examples of the surface treatment agent include vinyl silane-based coupling agents, (meth)acrylic acid-based coupling agents, fluorosilane coupling agents, amino silane-based coupling agents, epoxy silane-based coupling agents, mercapto silane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, etc. Among them, from the viewpoint of significantly obtaining the effects of the present invention, vinyl silane-based coupling agents, (meth)acrylic acid-based coupling agents, amino silane-based coupling agents, epoxy silane-based coupling agents, and silane-based coupling agents are preferred, and amino silane-based coupling agents, epoxy silane-based coupling agents, and silane-based coupling agents are more preferred. In addition, the surface treatment agent can be used alone or in any combination of two or more.

[0074] Examples of commercially available surface treatment agents include, for example, "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-methacryloxypropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[0075] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a specified range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent, more preferably surface-treated with 0.2 parts by mass to 3 parts by mass of the surface treatment agent, and still more preferably surface-treated with 0.3 parts by mass to 2 parts by mass of the surface treatment agent.

[0076] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and still more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and still more preferably 0.5 mg / m 2 or less.

[0077] The carbon amount per unit surface area of the inorganic filler can be measured after subjecting the surface-treated inorganic filler to a cleaning treatment with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. etc. can be used.

[0078] From the viewpoint of effectively reducing the linear thermal expansion coefficient of the resin composition, when the non-volatile components in the resin composition are 100% by mass, the content (% by mass) of the component (C) is preferably 80% by mass or more, more preferably 83% by mass or more, still more preferably 85% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, and still more preferably 90% by mass or less. In the present invention, even when the resin composition contains a large amount of inorganic filler, the adhesion after the HAST test can be maintained, so that both the reduction of the thermal expansion coefficient and the improvement of the adhesion to the conductor layer after the HAST test can be achieved.

[0079] <(D) Curing accelerator>

[0080] The resin composition may contain (D) a curing accelerator as an optional component. As the curing accelerator, for example, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, etc. can be cited. Preferably, an amine-based curing accelerator and an imidazole-based curing accelerator are used, and more preferably, an amine-based curing accelerator is used. The curing accelerator can be used alone or in combination of two or more.

[0081] As the phosphorus-based curing accelerator, for example, triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium caprylate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. can be cited. Preferably, triphenylphosphine and tetrabutylphosphonium caprylate are used.

[0082] As the amine-based curing accelerator, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. can be cited. Preferably, 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are used.

[0083] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine 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-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins. Preferably, they are 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

[0084] As the imidazole-based curing accelerator, commercially available products can be used. Examples include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0085] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. Preferably, they are dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0086] As the metal-based curing accelerator, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. can be cited. As specific examples of the organometallic complexes, organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, organomanganese complexes such as manganese(II) acetylacetonate, etc. can be cited. As the organometallic salts, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited, for example.

[0087] When the non-volatile components in the resin composition are set to 100% by mass, the content of the (C) curing accelerator is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, particularly preferably 0.05% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0088] <(E) Other additives>

[0089] In addition to containing the above components, the resin composition may further contain other additives as optional components. As such additives, for example, thermoplastic resins; flame retardants; organic fillers; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thickeners; defoamers; leveling agents; adhesion imparting agents; colorants; pigments and other resin additives can be cited. These additives can be used alone or two or more of them can be used in any ratio in combination.

[0090] As colorants and pigments, for example, fine particles such as melamine and organobentonite; phthalocyanine blue; phthalocyanine green; iodine green; diazo yellow; crystal violet; titanium oxide; carbon black such as "MA-600MJ-S)" manufactured by Mitsubishi Chemical Corporation; naphthol black, etc. can be cited.

[0091] When the non-volatile components in the resin composition are set to 100% by mass, the content of the colorant and pigment is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0092] The above resin composition may contain a solvent as needed, but is preferably a solvent-free resin composition that is substantially free of solvents. Even without such a solvent, the above resin composition can be fluidized when formed by a compression molding method, and excellent compression moldability can be achieved. Therefore, this resin composition can be used as a solvent-free resin composition. "Substantially free of solvents" means that, for example, the content of the solvent is 1% by mass or less relative to the entire solvent-free resin composition.

[0093] <Method for Manufacturing Resin Composition>

[0094] The resin composition of the present invention can be manufactured, for example, by a method of stirring the compounding components using a stirring device such as a rotary mixer. As described above, it is preferable to remove epichlorohydrin, which is the main component of impurities, from the (A) epoxy resin before manufacturing the resin composition. In addition, if necessary, it is also preferable to remove the impurities contained in the components (B) to (E).

[0095] <Properties and Physical Properties of Resin Composition>

[0096] The resin composition of the present invention can be in a liquid state or a solid state, but it is preferably in a liquid state during its molding. For example, a resin composition that is in a liquid state at normal temperature (e.g., 20°C) can be molded using a compression molding method at normal temperature without special temperature adjustment, or can be heated to an appropriate temperature and then molded using a compression molding method. In addition, a resin composition that is in a liquid state at normal temperature can be filled into a cylinder, the resin composition can be discharged from the cylinder, and then molded using a compression molding method. In addition, a resin composition that is in a solid state at normal temperature usually becomes a liquid state by adjusting its temperature to a higher temperature (e.g., 130°C), so it can be molded using a compression molding method by appropriate temperature adjustment such as heating. The above-mentioned resin composition can usually become a liquid state even without containing a solvent at an appropriate temperature, and can be used as a liquid sealing material, for example.

[0097] Here, the liquid state means that the lowest melt viscosity of the resin composition is 4000 poise or less. The detailed value of the lowest melt viscosity of the resin composition is preferably 4000 poise or less, more preferably 3000 poise or less, still more preferably 2000 poise or less, preferably 50 poise or more, more preferably 60 poise or more, still more preferably 70 poise or more. Here, the term "lowest melt viscosity" means the lowest melt viscosity at 60°C to 200°C. The lowest melt viscosity can be measured using a dynamic viscoelasticity measuring device. The measurement of the above-mentioned lowest melt viscosity can be carried out according to the method described in the following examples.

[0098] The cured product obtained by thermally curing the resin composition of the present invention at 180°C for 90 minutes usually exhibits the characteristic of a low coefficient of thermal expansion. Therefore, the above-mentioned cured product provides a sealing layer or insulating layer with a low coefficient of thermal expansion. The coefficient of thermal expansion is preferably 15 ppm or less, more preferably 10 ppm or less, still more preferably 9 ppm or less. On the other hand, the lower limit value of the coefficient of thermal expansion can be set to 1 ppm or more, etc. The measurement of the coefficient of thermal expansion can be carried out according to the method described in the following examples.

[0099] The cured product obtained by thermally curing the resin composition of the present invention at 180°C for 90 minutes has a high shear strength with copper after the HAST test, and thus exhibits excellent copper adhesion after the HAST test. Therefore, the above-mentioned cured product provides a sealing layer or insulating layer with excellent copper adhesion after the HAST test. The shear strength after the HAST test is preferably 0.5 kgf / mm 2 or more, more preferably 0.6 kgf / mm 2 or more, and even more preferably 0.7 kgf / mm 2 or more. On the other hand, the upper limit value of the shear strength can be set to 10 kgf / mm 2 or less, etc. The evaluation of the copper adhesion after the HAST test can be measured according to the method described in the following examples.

[0100] The chloride ion content of the resin composition of the present invention is 50 ppm or less, preferably 40 ppm or less, more preferably 30 ppm or less, and even more preferably 25 ppm or less. By making the chloride ion content within the above range, a cured product with excellent adhesion to the conductor layer even after the HAST test can be obtained. The lower limit of the chloride ion content is not particularly limited and can be set to 0 ppm or more, 0.1 ppm or more, etc. The chloride ion content is measured by the sample combustion - ion chromatography method (BS EN 14582 2007).

[0101] Due to the above characteristics, the resin composition can be suitably used as a resin composition for sealing electronic devices such as organic EL devices and semiconductors (resin composition for sealing), and in particular, can be suitably used as a resin composition for sealing semiconductors (resin composition for semiconductor sealing), preferably a resin composition for sealing semiconductor chips (resin composition for semiconductor chip sealing). In addition, in addition to the sealing use, the resin composition can be used as a resin composition for an insulating layer. For example, the above resin composition can be suitably used as a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for insulating layer of semiconductor chip package) and a resin composition for forming an insulating layer of a circuit board (including printed wiring board) (resin composition for insulating layer of circuit board).

[0102] Examples of semiconductor chip packages include: FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package), and fan-in type PLP.

[0103] In addition, the above resin composition can be used as an underfill material, for example, it can be used as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

[0104] Furthermore, the above resin composition can be used in the following wide range of applications where a resin composition can be used: sheet-like laminated materials such as resin sheets and prepregs, solder resists, chip bonding materials, via filling resins, component embedding resins, etc.

[0105] [Resin sheet]

[0106] 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 from the resin composition.

[0107] From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, still more preferably 500 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, or 200 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited and can be, for example, 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0108] Examples of the support include a film formed of a plastic material, a metal foil, and a release paper, and preferably a film formed of a plastic material or a metal foil.

[0109] When using a film formed of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET") and polyethylene naphthalate (hereinafter sometimes simply referred to as "PEN"); polycarbonate (hereinafter sometimes simply referred to as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes simply referred to as "PMMA"); cyclic polyolefins; triacetyl cellulose (hereinafter sometimes simply referred to as "TAC"); polyether sulfide (hereinafter sometimes simply referred to as "PES"); polyether ketone; polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0110] When using a metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc. Among them, copper foil is preferred. As the copper foil, a foil formed of a single metal of copper or a foil formed of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0111] For the support, the surface that is joined to the resin composition layer can be subjected to treatments such as matte treatment, corona treatment, and antistatic treatment.

[0112] In addition, as the support, a support with a release layer having a release layer on the surface joined to the resin composition layer can be used. As the release agent used in the release layer of the support with a release layer, one or more release agents selected from, for example, alkyd resins, polyolefin resins, polyurethane resins, and silicone resins can be cited. As commercially available products of release agents, for example: "SK-1", "AL-5", "AL-7", etc. manufactured by Lintec Corporation as alkyd resin-based release agents. In addition, as the support with a release layer, for example: "LUMIRROR T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipeel" manufactured by UNITIKA Ltd., etc. can be cited.

[0113] The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. It should be noted that in the case of using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0114] The resin sheet can be produced, for example, by coating a resin composition on a support using a coating device such as a die coater. In addition, if necessary, the resin composition can be dissolved in an organic solvent to prepare a resin varnish, and the resin sheet can be produced by coating the resin varnish. By using a solvent, the viscosity can be adjusted and the coatability can be improved. In the case of using a resin varnish, usually the resin varnish is dried after coating to form a resin composition layer.

[0115] As the organic solvent, for example: ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone, etc. The organic solvent can be used alone or two or more kinds can be used in any ratio in combination.

[0116] The drying can be carried out by known methods such as heating and hot air blowing. Regarding the drying conditions, drying is carried out under the condition that the content of the organic solvent in the resin composition layer usually becomes 10% by mass or less, preferably 5% by mass or less. 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% to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0117] The resin sheet may optionally contain any layer other than the support and the resin composition layer as needed. For example, in the resin sheet, a protective film selected according to the support may be provided on the surface of the resin composition layer that is not joined to the support (i.e., the surface on the side opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. By using the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, the resin sheet can be wound into a roll for storage.

[0118] The resin sheet can be suitably used for: forming an insulating layer in the manufacture of semiconductor chip packages (resin sheet for insulation of semiconductor chip packages). For example, the resin sheet can be used to form an insulating layer of a circuit board (resin sheet for insulating layer of a circuit board). Examples of packages using such a substrate include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

[0119] In addition, the resin sheet can be suitably used to seal semiconductor chips (resin sheet for sealing semiconductor chips). Examples of applicable semiconductor chip packages include, for example, fan-out WLP, fan-in WLP, fan-out PLP, fan-in PLP, etc.

[0120] In addition, the resin sheet can be used as a material for MUF used after connecting a semiconductor chip to a substrate.

[0121] Furthermore, the resin sheet can be used for other wide-ranging applications that require high insulation reliability. For example, the resin sheet can be suitably used to form an insulating layer of a circuit board such as a printed wiring board.

[0122] [Circuit Board]

[0123] The circuit board of the present invention includes an insulating layer formed of 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).

[0124] (1) A step of forming a resin composition layer on a substrate;

[0125] (2) A step of thermally curing the resin composition layer to form an insulating layer.

[0126] In step (1), a base material is prepared. Examples of the base material include a glass epoxy substrate, a metal substrate (such as stainless steel, cold-rolled steel sheet (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, for the base material, as a part of the base material, a metal layer such as a copper foil may be provided on the surface. For example, a base material having a peelable first metal layer and a second metal layer on both surfaces may also be used. When using such a base material, generally, as the conductor layer that can function as a circuit wiring, it can be formed on the surface of the second metal layer opposite to the first metal layer. Examples of the material of the metal layer include copper foil, copper foil with a carrier, and the material of the following conductor layer, and preferably copper foil. In addition, as the base material having such a metal layer, commercially available products can be used. For example, the ultra-thin copper foil "Micro Thin" of the copper foil with a carrier manufactured by Mitsui Mining & Smelting Co., Ltd. can be cited.

[0127] In addition, a conductor layer can be formed on one or both surfaces of the base material. In the following description, a member including the base material and the conductor layer formed on the surface of the base material may be appropriately referred to as a "base material with a wiring layer". Examples of the conductor material included in the conductor layer include materials containing one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductor material, a single metal can be used, or an alloy can be used. Examples of the alloy include alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of the generality of conductor layer formation, cost, ease of pattern formation, etc., preferably, as a single metal, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and as an alloy, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy. Among them, more preferably, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel-chromium alloy; particularly preferably, a single metal of copper.

[0128] For the conductor layer, for example, in order to function as a wiring layer, pattern processing can be performed. At this time, the line width (circuit width) / line pitch (width between circuits) ratio of the conductor layer is not particularly limited, preferably 20 / 20 μm or less (that is, the pitch is 40 μm or less), more preferably 10 / 10 μm or less, further preferably 5 / 5 μm or less, still further preferably 1 / 1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not need to be the same throughout the conductor layer. The minimum pitch of the conductor layer can be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

[0129] The thickness of the conductor layer varies depending on the design of the circuit board, but is preferably from 3 μm to 35 μm, more preferably from 5 μm to 30 μm, further preferably from 10 μm to 20 μm, particularly preferably from 15 μm to 20 μm.

[0130] The conductor layer can be formed, for example, by a method comprising the following steps: a step of laminating a dry film (photosensitive resist film) on a substrate; a step of exposing and developing the dry film under prescribed conditions using a photomask to form a pattern, thereby obtaining a pattern dry film; a step of 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 step of stripping the pattern dry film. As the dry film, a photosensitive dry film formed by a photoresist composition can be used, for example, a dry film formed by a resin such as a novolac resin or an acrylic resin can be used. The lamination conditions of the substrate and the dry film can be the same as the lamination conditions of the substrate and the resin sheet described later. The stripping of the dry film can be implemented, for example, by using an alkaline stripping solution such as a sodium hydroxide solution.

[0131] After preparing the substrate, the resin composition layer is formed on the substrate. When the conductor layer is formed on the surface of the substrate, the resin composition layer is preferably formed so that the conductor layer is buried in the resin composition layer.

[0132] The formation of the resin composition layer is carried out, for example, by laminating a resin sheet with a substrate. The lamination can be carried out, for example, by the following method: the resin sheet is heated and pressed to the substrate from the support body side, thereby the resin composition layer is attached to the substrate. As a component (hereinafter sometimes referred to as "heating and pressing component") for heating and pressing the resin sheet to the substrate, for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller, etc.) can be cited. It should be noted that it is better not to directly press the heating and pressing component to the resin sheet, but to make the resin sheet fully conform to the surface unevenness of the substrate, and to press it across an elastic material such as heat-resistant rubber.

[0133] The lamination of the substrate and the resin sheet can be implemented, for example, by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa. The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably implemented under reduced pressure conditions of 13hPa or less.

[0134] After lamination, under normal pressure (atmospheric pressure), for example, the heated crimping member can be pressed from the support body side to perform a smoothing process on the laminated resin sheet. The pressing conditions for the smoothing process can be the same as those for the above-mentioned heated crimping during lamination. It should be noted that lamination and the smoothing process can be continuously performed using a vacuum laminator.

[0135] In addition, the formation of the resin composition layer can be carried out, for example, by a compression molding method. For the specific operation of the compression molding method, for example, as a mold, an upper mold and a lower mold are prepared. The resin composition is coated on the substrate. The substrate coated with the resin composition is mounted on the lower mold. Then, the upper mold and the lower mold are closed, heat and pressure are applied to the resin composition, and compression molding is performed.

[0136] In addition, the specific operation of the compression molding method can also be carried out as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. The resin composition is placed on the lower mold. In addition, the substrate is mounted on the upper mold. Then, the upper mold and the lower mold are closed in such a way that the resin composition placed on the lower mold contacts the substrate mounted on the upper mold, heat and pressure are applied, and compression molding is performed.

[0137] The molding conditions in the compression molding method vary depending on the composition of the resin composition. The temperature of the mold during molding is preferably a temperature at which the resin composition can exhibit excellent compression moldability. For example, it is preferably 80 °C or higher, more preferably 100 °C or higher, still more preferably 120 °C or higher, preferably 200 °C or lower, more preferably 170 °C or lower, still more preferably 150 °C or lower. In addition, the pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, still more preferably 5 MPa or higher, preferably 50 MPa or lower, more preferably 30 MPa or lower, still more preferably 20 MPa or lower. The curing time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, preferably 60 minutes or shorter, more preferably 30 minutes or shorter, particularly preferably 20 minutes or shorter. Usually, after forming the resin composition layer, the mold is removed. The removal of the mold can be carried out before or after the thermal curing of the resin composition layer.

[0138] After forming the resin composition layer on the substrate, the resin composition layer is thermally cured to form an insulating layer. Although the thermal curing conditions of the resin composition layer also vary depending on the type of the resin composition, the curing temperature is generally in the range of 120 °C to 240 °C (preferably in the range of 150 °C to 220 °C, more preferably in the range of 170 °C to 200 °C), and the curing time is in the range of 5 minutes to 120 minutes (preferably in the range of 10 minutes to 100 minutes, more preferably in the range of 15 minutes to 90 minutes).

[0139] Before the resin composition layer is thermally cured, a preheating treatment of heating the resin composition layer at a temperature lower than the curing temperature can be performed. For example, before the resin composition layer is thermally cured, the resin composition layer can be preheated at a temperature generally of 50°C or higher and lower than 120°C (preferably 60°C or higher and 110°C or lower, more preferably 70°C or higher and 100°C or lower) for generally 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

[0140] By operating as described above, a circuit board having an insulating layer can be manufactured. In addition, the manufacturing method of the circuit board can further include any process. For example, when manufacturing a circuit board using a resin sheet, the manufacturing method of the circuit board can include a process of peeling the support of the resin sheet. The support can be peeled before the resin composition layer is thermally cured, or the support can be peeled after the resin composition layer is thermally cured.

[0141] The manufacturing method of the circuit board can, for example, include a process of grinding the surface of the insulating layer after the insulating layer is formed. The grinding method is not particularly limited. For example, a surface grinder can be used to grind the surface of the insulating layer.

[0142] The manufacturing method of the circuit board can, for example, include a process (3) of interlayer connection of the conductor layer, that is, a process of opening holes in the insulating layer. Thereby, holes such as vias and through-holes can be formed in the insulating layer. As a method for forming vias, for example, laser irradiation, etching, mechanical drilling, etc. can be cited. The size and shape of the vias can be appropriately determined according to the design of the circuit board. It should be noted that for process (3), interlayer connection can be performed by grinding or grinding the insulating layer.

[0143] After the vias are formed, it is preferable to perform a process of removing the smear in the vias. This process is sometimes called the smear removal process. For example, in the case where the conductor layer is formed on the insulating layer through a plating process, a wet smear removal treatment can be performed on the vias. In addition, in the case where the conductor layer is formed on the insulating layer through a sputtering process, a dry smear removal process such as a plasma treatment process can be performed. Furthermore, the insulating layer can also be roughened by the smear removal process.

[0144] In addition, before forming the conductor layer on the insulating layer, the insulating layer can be roughened. Through this roughening treatment, generally, the surface of the insulating layer including the inside of the vias can be roughened. As the roughening treatment, any dry and wet roughening treatment can be performed. As an example of the dry roughening treatment, plasma treatment, etc. can be cited. In addition, as an example of the wet roughening treatment, a method of sequentially performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidant, and a neutralization treatment using a neutralization liquid can be cited.

[0145] After forming the through-holes, a conductor layer is formed on the insulating layer. By forming the conductor layer at the positions where the through-holes are formed, the newly formed conductor layer is electrically connected to the conductor layer on the substrate surface, enabling interlayer connection. As for the method of forming the conductor layer, for example, plating methods, sputtering methods, evaporation plating methods, etc. can be cited, among which the plating method is preferably used. In a preferred embodiment, an appropriate method such as semi-additive method or full-additive method is used to perform plating on the surface of the insulating layer to form a conductor layer with a desired wiring pattern. In addition, when the support in the resin sheet is a metal foil, a subtractive method can be used to form a conductor layer with a desired wiring pattern. The material of the formed conductor layer can be a single metal or an alloy. In addition, the conductor layer can have a single-layer structure or a multi-layer structure including layers of two or more different materials.

[0146] Here, an example of an embodiment of forming a conductor layer on the insulating layer will be described in detail. By electroless plating, a plating seed layer is formed on the surface of the insulating layer. Next, corresponding to the desired wiring pattern, a mask pattern that exposes a part of the plating seed layer is formed on the formed plating seed layer. By electroplating, an electroplated layer is formed on the exposed plating seed layer, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or other processes, and a conductor layer with a desired wiring pattern can be formed. It should be noted that when forming the conductor layer, the dry film used in the formation of the mask pattern is the same as the above-mentioned dry film.

[0147] The method for manufacturing a circuit board may include a step (4) of removing the substrate. By removing the substrate, a circuit board having an insulating layer and a conductor layer buried in the insulating layer can be obtained. Regarding this step (4), for example, it can be performed in the case of using a substrate having a peelable metal layer.

[0148] [Semiconductor Chip Package]

[0149] The semiconductor chip package according to the first embodiment of the present invention includes the above-mentioned circuit board and a semiconductor chip mounted on the circuit board. This semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit board.

[0150] Regarding the bonding conditions between the circuit board and the semiconductor chip, any conditions under which the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board can be conductively connected can be adopted. For example, the conditions used in flip-chip mounting of the semiconductor chip can be adopted. In addition, for example, between the semiconductor chip and the circuit board, bonding can be performed via an insulating adhesive.

[0151] As an example of the bonding method, a method of pressing a semiconductor chip onto a circuit board can be cited. As the pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the pressing time is usually in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

[0152] In addition, as other examples of the bonding method, a method of bonding a semiconductor chip to a circuit board by reflow soldering can be cited. The reflow soldering conditions can be in the range of 120°C to 300°C.

[0153] After bonding the semiconductor chip to the circuit board, the semiconductor chip can be filled with a molding underfill material. As the molding underfill material, the above resin composition can be used, and in addition, the above resin sheet can be used.

[0154] The semiconductor chip package according to the second embodiment of the present invention includes a semiconductor chip and a cured product of the above resin composition that seals the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition usually functions as a sealing layer. As the semiconductor chip package according to the second embodiment, for example, a fan-out type WLP can be cited.

[0155] The manufacturing method of such a semiconductor chip package such as a fan-out type WLP includes the following steps:

[0156] (A) A step of laminating a temporary fixing film on a substrate,

[0157] (B) A step of temporarily fixing a semiconductor chip on the temporary fixing film,

[0158] (C) A step of laminating the resin composition of the resin sheet of the present invention layer by layer on the semiconductor chip, or coating the resin composition of the present invention on the semiconductor chip, and performing thermal curing to form a sealing layer,

[0159] (D) A step of peeling the substrate and the temporary fixing film from the semiconductor chip,

[0160] (E) A step of forming a redistribution formation layer (insulating layer) on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled,

[0161] (F) A step of forming a conductor layer (redistribution layer) on the redistribution formation layer (insulating layer), and

[0162] (G) A step of forming a solder resist layer on the conductor layer. In addition, the manufacturing method of the semiconductor chip package may include the following steps:

[0163] (H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages for singulation.

[0164] For the details of the manufacturing method of such a semiconductor chip package, reference can be made to paragraphs 0066 to 0081 of International Publication No. 2016 / 035577, the content of which is incorporated herein by reference.

[0165] The semiconductor chip package according to the third embodiment of the present invention is, for example, a semiconductor chip package in which a cured product of the resin composition of the present invention is used to form a redistribution layer or a solder resist layer in the semiconductor chip package of the second embodiment.

[0166] [Semiconductor Device]

[0167] Examples of the semiconductor device on which the above semiconductor chip package is mounted include various semiconductor devices for electrical products (such as computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and transportation means (such as motorcycles, automobiles, trains, ships, and airplanes). Examples

[0168] Hereinafter, examples will be shown to specifically illustrate the present invention. However, the present invention is not limited to the following examples. In the following description, "ppm", "parts", and "%" indicating amounts are on a mass basis unless otherwise clearly specified. In addition, unless otherwise clearly specified, the operations described below are performed in an environment of normal temperature and pressure.

[0169] The epoxy resin used in the examples is an epoxy resin purified by distilling a commercially available product. In addition, silica A, silica B, and silica C used in the examples and comparative examples are as follows:

[0170] Silica A: silica having an average particle diameter of 9.2 μm, a specific surface area of 3.3 m 2 / g and surface-treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane);

[0171] Silica B: silica having an average particle diameter of 8.5 μm, a specific surface area of 3.2 m 2 / g and surface-treated with KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane);

[0172] Silica C: silica having an average particle diameter of 9.6 μm, a specific surface area of 2.9 m 2 / g and surface-treated with KBM4803 (manufactured by Shin-Etsu Chemical Co., Ltd., long-chain epoxy type silane coupling agent).

[0173] <Example 1>

[0174] 5 parts of glycidylamine epoxy resin (epoxy equivalent: 95 g / eq.), 5 parts of bisphenol epoxy resin (a 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent: 169 g / eq.), 7 parts of acid anhydride curing agent (manufactured by Shin Nippon Rika Co., Ltd., "MH-700", acid anhydride equivalent: 164 g / eq.), 140 parts of silica A, 0.1 part of curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ", 1-benzyl-2-phenylimidazole), and 0.6 part of carbon black (manufactured by Mitsubishi Chemical Corporation, "MA-600MJ-S") were mixed and uniformly dispersed in a mixer to prepare Resin Composition 1.

[0175] <Example 2>

[0176] In Example 1, silica A was changed to silica B. Except for the above, the same operations as in Example 1 were performed to prepare Resin Composition 2.

[0177] <Example 3>

[0178] In Example 1, silica A was changed to silica C. Except for the above, the same operations as in Example 1 were performed to prepare Resin Composition 3.

[0179] <Example 4>

[0180] In Example 1, the amount of bisphenol epoxy resin (a 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent: 169 g / eq.) was changed from 5 parts to 2 parts, and further 3 parts of alicyclic epoxy resin (epoxy equivalent: 136 g / eq.) was used. Except for the above, the same operations as in Example 1 were performed to prepare Resin Composition 4.

[0181] <Comparative Example 1>

[0182] In Example 1,

[0183] 5 parts of glycidylamine epoxy resin (epoxy equivalent: 95 g / eq.) was changed to 5 parts of glycidylamine epoxy resin (manufactured by Mitsubishi Chemical Corporation, "630", epoxy equivalent: 95 g / eq.),

[0184] 5 parts of bisphenol epoxy resin (a 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent: 169 g / eq.) was changed to 5 parts of bisphenol F epoxy resin (manufactured by Nagase ChemteX Corporation, "EX-211", epoxy equivalent: 138 g / eq.),

[0185] Except for the above, the same operations as in Example 1 were performed to prepare Resin Composition 5. It should be noted that in Comparative Example 1, "630" and "EX-211" were not distilled and the commercially available products were used directly.

[0186] <Determination of chloride ion content>

[0187] The chloride ion content of the resin compositions 1 to 5 prepared in the examples and comparative examples was determined using combustion-ion chromatography (in accordance with BS EN 14582 2007).

[0188] <Determination of coefficient of thermal expansion (CTE)>

[0189] On a demolded 12-inch silicon wafer, the resin compositions 1 to 5 prepared in the examples and comparative examples were compression molded using a compression molding device (mold temperature: 130 °C, pressure: 6 MPa, curing time: 10 minutes) to form a resin composition layer with a thickness of 300 μm. Then, the resin composition layer was peeled off from the demolded silicon wafer and heat cured by heating at 180 °C for 90 minutes to produce a cured sample. The cured sample was cut into a width of 5 mm and a length of 15 mm to obtain test pieces. For these test pieces, a thermomechanical analysis was performed using a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Corporation) by the tensile load method. Specifically, after the test piece was assembled in the above thermomechanical analysis device, it was continuously measured twice under the measurement conditions of a load of 1 g and a heating rate of 5 °C / minute. Then, the coefficient of thermal expansion (ppm / °C) in the planar direction in the range from 25 °C to 150 °C in the second measurement was calculated.

[0190] <Determination of minimum melt viscosity>

[0191] For the resin compositions 1 to 5 prepared in the examples and comparative examples, the minimum melt viscosity was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Corporation). For 1 g of the sample resin composition, a parallel plate with a diameter of 18 mm was used, and the temperature was raised from the starting temperature of 60 °C to 200 °C at a heating rate of 5 °C / minute. The dynamic viscoelastic modulus was measured under the measurement conditions of a measurement temperature interval of 2.5 °C, a vibration frequency of 1 Hz, and a deformation of 1 deg to obtain the value of the minimum melt viscosity.

[0192] <Evaluation of copper adhesion after HAST test>

[0193] On the copper surfaces of a glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.4 mm, "R1515A" manufactured by Panasonic Corporation), specimens were formed such that the resin compositions prepared in the examples and comparative examples had a diameter of 4 mm and a height of 5 mm. Specifically, a silicone rubber frame with a diameter of 4 mm was dug out, and the resin composition was filled to form a cylindrical shape with a height of 5 mm. After heating at 180 °C for 90 minutes, the silicone rubber frame was removed to fabricate the specimens. After subjecting the specimens to a high-temperature and high-humidity environment test (HAST) under the conditions of 130 °C, 85% RH, and 96 hours, the shear strength of the interface between the copper and the specimens was measured using a bond tester (manufactured by Dage Co., Ltd., series 4000) under the conditions that the head position was 1 mm away from the substrate and the head speed was 700 μm / s. Five tests were conducted, and the average value was used. When the shear strength was 0.5 kgf / mm 2 or more, it was evaluated as "〇", and when the shear strength was less than 0.5 kgf / mm 2 , it was evaluated as "×".

[0194] [Table 1]

[0195] .

[0196] It was confirmed that in Examples 1 to 4, even when the components (D) to (E) were not contained, although there were differences in degree, the same results as those of the above examples were obtained.

Claims

1. A circuit board, comprising: a copper-containing conductor layer and an insulating layer formed of a cured product of a resin composition, wherein, the insulating layer is in close contact with copper, the resin composition contains (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a curing accelerator, the component (A) contains an aromatic epoxy resin, the component (A) contains an epoxy resin that is liquid at 20 °C, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (A) is 15% by mass or less, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (C) is 90% by mass or less, the resin composition is liquid at 20 °C, the amount of chloride ions contained in the resin composition, measured according to BS EN 14582 2007 by the sample combustion - ion chromatography method, is 50 ppm or less.

2. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (A) is 1% by mass or more.

3. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (A) is 5% by mass or more.

4. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (A) is 10% by mass or less.

5. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (B) is 1% by mass or more.

6. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (B) is 3% by mass or more.

7. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (B) is 10% by mass or less.

8. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (B) is 5% by mass or less.

9. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (C) is 80% by mass or more.

10. The circuit board according to claim 1, wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (C) is 85% by mass or more.

11. The circuit board according to claim 1, wherein, the amount of chloride ions contained in the resin composition, measured according to BS EN 14582 2007 by the sample combustion - ion chromatography method, is 25 ppm or less.

12. The circuit board according to claim 1, wherein, the amount of chloride ions contained in the resin composition, measured according to BS EN 14582 2007 by the sample combustion - ion chromatography method, is 0.1 ppm or more.

13. The circuit board according to claim 1, wherein, The coefficient of thermal expansion of the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes is 15 ppm or less.

14. The circuit board according to claim 1, wherein, The coefficient of thermal expansion of the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes is 9 ppm or less.

15. The circuit board according to claim 1, wherein, The coefficient of thermal expansion of the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes is 1 ppm or more.

16. The circuit board according to claim 1, wherein, (Component B) contains an acid anhydride-based curing agent.

17. A resin composition, which is a resin composition containing (A) epoxy resin, (B) curing agent, (C) inorganic filler, and (D) curing accelerator, (Component A) contains a distilled epoxy resin, (Component A) contains an aromatic epoxy resin, (Component A) contains an epoxy resin that is liquid at a temperature of 20°C, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component C) is 90% by mass or less, The resin composition is liquid at a temperature of 20°C, The amount of chloride ions contained in the resin composition, measured according to the test method of combustion-ion chromatography BS EN 14582 2007, is 50 ppm or less.

18. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component A) is 1% by mass or more.

19. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component A) is 5% by mass or more.

20. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component A) is 20% by mass or less.

21. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component A) is 10% by mass or less.

22. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component B) is 1% by mass or more.

23. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component B) is 3% by mass or more.

24. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component B) is 10% by mass or less.

25. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component B) is 5% by mass or less.

26. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are set to 100% by mass, the content of (Component C) is 80% by mass or more.

27. The resin composition according to claim 17, wherein, When the non-volatile components in the resin composition are 100% by mass, the content of component (C) is 85% by mass or more.

28. The resin composition according to claim 17, wherein the amount of chloride ions contained in the resin composition, as measured by the test specimen combustion-ion chromatography method BS EN 14582 2007, is 25 ppm or less.

29. The resin composition according to claim 17, wherein the amount of chloride ions contained in the resin composition, as measured by the test specimen combustion-ion chromatography method BS EN 14582 2007, is 0.1 ppm or more.

30. The resin composition according to claim 17, wherein the coefficient of thermal expansion of the cured product obtained by thermally curing the resin composition at 180 °C for 90 minutes is 15 ppm or less.

31. The resin composition according to claim 17, wherein the coefficient of thermal expansion of the cured product obtained by thermally curing the resin composition at 180 °C for 90 minutes is 9 ppm or less.

32. The resin composition according to claim 17, wherein the coefficient of thermal expansion of the cured product obtained by thermally curing the resin composition at 180 °C for 90 minutes is 1 ppm or more.

33. The resin composition according to claim 17, wherein component (B) contains an acid anhydride-based curing agent.

34. The resin composition according to claim 17, which is a resin composition for sealing or for an insulating layer.

35. A circuit board, which comprises an insulating layer formed by using the cured product of the resin composition according to any one of claims 17 to 34.

36. A semiconductor chip package, which comprises: the circuit board according to any one of claims 1 to 16, 35, and a semiconductor chip mounted on the circuit board.

37. A semiconductor chip package, which comprises: a semiconductor chip, and the cured product of the resin composition according to any one of claims 17 to 34 for sealing the semiconductor chip.