Resin composition
Patent Information
- Application Number
- JP2024090094
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-06-03
- Publication Date
- 2025-06-10
- Estimated Expiration
- 2039-03-07
AI Technical Summary
The adhesion between insulating layers and conductor layers in electronic devices decreases after high temperature and high humidity environmental tests due to the incorporation of inorganic fillers in resin compositions, leading to potential delamination issues.
A resin composition with reduced chloride ions (50 ppm or less) and a high content of inorganic filler (80% by mass) is used, along with a thermal curing process at 180°C for 90 minutes, to enhance adhesion and reduce thermal expansion.
The composition maintains excellent adhesion to conductor layers even after high temperature and humidity tests, while reducing thermal expansion, making it suitable for sealing and insulating layers in electronic devices.
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Figure 2024107044000001
Abstract
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 technology]
[0002] In recent years, the demand for small, highly functional electronic devices such as smartphones and tablet devices has been increasing, and accordingly, insulating materials that can be used as sealing layers or insulating layers for these small electronic devices are required to have higher functionality. As such insulating materials, for example, those formed by curing a resin composition are known (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]
[0003] [Patent Document 1] JP 2013-237715 A [Patent Document 2] Patent No. 6288344 Summary of the Invention [Problem to be solved by the invention]
[0004] The present inventors have investigated resin compositions capable of forming a sealing layer or an insulating layer, and have found that while the coefficient of thermal expansion (sometimes referred to as "CTE") can usually be reduced by adding an inorganic filler to a resin composition, when an environmental test (HAST test) is performed in a high temperature and high humidity environment, the adhesion between the insulating layer and a conductor layer such as copper foil is reduced.
[0005] The present invention has been devised in view of the above-mentioned problems, and has an object to provide a resin composition that is capable of giving a cured product that has excellent adhesion to a conductor layer even after HAST testing; and a circuit board and a semiconductor chip package that use the resin composition. [Means for solving the problem]
[0006] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors discovered that by controlling the amount of chloride ions contained in a resin composition to a certain value or less, a cured product having excellent adhesion to a conductor layer can be obtained even after a HAST test, and thus completed the present invention.
[0007] That is, the present invention includes the following. [1] (A) epoxy resin, (B) a curing agent, and (C) a resin composition containing an inorganic filler, A resin composition, the amount of chloride ions contained in the resin composition being 50 ppm or less as measured in accordance with a sample combustion-ion chromatography method (BS EN 14582 2007). [2] The resin composition according to [1], wherein the content of component (C) is 80 mass% or more, based on 100 mass% of the non-volatile components in the resin composition. [3] The resin composition according to [1] or [2], wherein the thermal expansion coefficient of the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes is 15 ppm or less. [4] The resin composition according to any one of [1] to [3], wherein the component (B) contains an acid anhydride curing agent. [5] The resin composition according to any one of [1] to [4], wherein the resin composition is liquid. [6] The resin composition according to any one of [1] to [5], which is a resin composition for sealing or insulating layers. [7] A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [6]. [8] A semiconductor chip package comprising the circuit board described in [7] and a semiconductor chip mounted on the circuit board. [9] A semiconductor chip package comprising: a semiconductor chip; and a cured product of the resin composition according to any one of [1] to [6] that encapsulates the semiconductor chip. Effect of the Invention
[0008] According to the present invention, it is possible to provide a resin composition which is capable of giving a cured product which has excellent adhesion to a conductor layer even after HAST testing; and a circuit board and a semiconductor chip package which use the resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0009] The present invention will be described in detail below with reference to the following embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and may be modified as desired without departing from the scope of the claims of the present invention and its equivalents. In addition, "ppm" is based on mass unless otherwise specified.
[0010] [Resin composition] 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, and the amount of chloride ions contained in the resin composition is 50 ppm or less as measured in accordance with a sample combustion-ion chromatography method (BS EN 14582 2007). By keeping the amount of chloride ions contained in the resin composition at 50 ppm or less, it is possible to obtain a cured product that has excellent adhesion to a conductor layer such as a copper foil even after a HAST test.
[0011] As described above, by adding a large amount of inorganic filler to the resin composition, the thermal expansion coefficient can be reduced, but the adhesion with the conductor layer after the HAST test decreases.
[0012] However, as a result of extensive research by the present inventors, it has been found that by setting the amount of chloride ions contained in the resin composition to 50 ppm or less, it is possible to improve the adhesion with the conductor layer after the HAST test.
[0013] The present inventors speculate that the mechanism by which the excellent advantages described above can be obtained by controlling the amount of chloride ions contained in the resin composition to 50 ppm or less is as follows, however, the technical scope of the present invention is not limited by the mechanism explained below. Component (A) may contain epichlorohydrin as an impurity. By removing this epichlorohydrin, corrosion of the conductor layer such as copper foil by the chloride ions of epichlorohydrin is suppressed. As a result, it is possible to obtain a cured product that has excellent adhesion to the conductor layer even after the HAST test. Therefore, the present invention is also advantageous in that it is possible to reduce the thermal expansion coefficient even if the resin composition contains a large amount of inorganic filler, and this can be simultaneously achieved while improving the adhesion with the conductor layer after the HAST test.
[0014] The resin composition may further contain optional components in combination with the components (A) to (C). Examples of the optional components include a curing accelerator (D) and other additives (E). Each component contained in the resin composition of the present invention will be described in detail below.
[0015] <(A) Epoxy resin> The resin composition contains an epoxy resin (A) as component (A). Examples of the epoxy resin (A) include 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, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, and tetraphenylethane type epoxy resin. The epoxy resin may be used alone or in combination of two or more kinds.
[0016] The resin composition preferably contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on 100% by mass of the non-volatile components of the epoxy resin (A).
[0017] Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may use a liquid epoxy resin as the epoxy resin (A), may use a solid epoxy resin, or may use a combination of a liquid epoxy resin and a solid epoxy resin. Of these, it is preferable to use a liquid epoxy resin from the viewpoint of reducing the viscosity of the resin composition.
[0018] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.
[0019] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins; alicyclic epoxy resins such as glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins such as alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, and more preferred are glycidyl amine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and alicyclic epoxy resins.
[0020] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidyl amine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "Nippon Steel & Sumitomo Metal Chemical Co., Ltd." Examples of such epoxy resins include "ZX1059" manufactured by Nagase ChemteX (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Daicel Corporation; "CEL-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" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "EP3950L" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation. These may be used alone or in combination of two or more types.
[0021] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.
[0022] As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and bisphenol AF type epoxy resin, biphenyl type epoxy resin, and bixylenol type epoxy resin are more preferred.
[0023] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; and "HP -7200HH, "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC 3000L, "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8" manufactured by Mitsubishi Chemical Co., Ltd. Examples of epoxy resins include "800" (anthracene type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals, "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical, "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical, "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical, and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical. These may be used alone or in combination of two or more.
[0024] However, the above-mentioned commercially available epoxy resins may contain epichlorohydrin. Therefore, commercially available epoxy resins are usually used after purification treatment to remove epichlorohydrin. This can reduce the amount of chloride ions in the resin composition. Examples of purification treatments include distillation.
[0025] When a liquid epoxy resin and a solid epoxy resin are used in combination as the (A) epoxy resin, the ratio of the amounts thereof (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, by mass. When the ratio of the liquid epoxy resin to the solid epoxy resin is within such a range, the desired effects of the present invention can be significantly obtained. Furthermore, when used in the form of a resin sheet, appropriate adhesion is usually obtained. Furthermore, when used in the form of a resin sheet, sufficient flexibility is usually obtained, and handling is improved. Furthermore, a cured product having sufficient breaking strength can usually be obtained.
[0026] The epoxy equivalent of the (A) epoxy resin is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, even more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. When it is in this range, the crosslink density of the cured product of the resin composition layer is sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent is the mass of a resin containing one equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.
[0027] The weight average molecular weight (Mw) of the (A) epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500, from the viewpoint of significantly achieving the desired effects of the present invention. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.
[0028] The content of the (A) epoxy resin is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulating reliability. 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, from the viewpoint of significantly obtaining the desired effects of the present invention. 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 taken as 100% by mass, unless otherwise specified.
[0029] From the viewpoint of keeping the amount of chloride ions in the resin composition at 50 ppm or less, it is usually preferable to distill the (A) epoxy resin before preparing the resin composition and remove epichlorohydrin, which is a main component of impurities in the (A) epoxy resin. The distillation temperature of the (A) epoxy resin, the pressure during distillation, etc. can be appropriately changed depending on the type of the (A) epoxy resin.
[0030] <(B) Hardener> The resin composition contains a (B) curing agent as the (B) component. The (B) curing agent usually has the function of reacting with the (A) component to cure the resin composition. The (B) curing agent may be used alone or in combination of two or more types.
[0031] Examples of the (B) curing agent include 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, and amine-based curing agents. Among these, from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to contain an acid anhydride-based curing agent.
[0032] Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples of acid anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid.
[0033] Commercially available acid anhydride curing agents include "MH-700" manufactured by New Japan Chemical Co., Ltd.
[0034] As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester curing agent, a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is preferred. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred.
[0035] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
[0036] Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.
[0037] Preferred specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene-type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated product of phenol novolac, and an active ester curing agent containing a benzoylated product of phenol novolac. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
[0038] Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "EXB-8000L-65TM" (manufactured by DIC Corporation) as active ester curing agents containing a dicyclopentadiene-type diphenol structure; "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester curing agents containing a naphthalene structure; and "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester curing agents containing an acetylated product of phenol novolac. Examples of such a hardener include "DC808" (manufactured by Mitsubishi Chemical Corporation); "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener containing a benzoyl derivative of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener which is an acetylated derivative of phenol novolac; and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester-based hardeners which are benzoyl derivatives of phenol novolac.
[0039] As the phenol-based curing agent and naphthol-based curing agent, those having a novolac structure are preferred from the viewpoint of heat resistance and water resistance, and from the viewpoint of adhesion to the conductor layer, nitrogen-containing phenol-based curing agents are preferred, and triazine skeleton-containing phenol-based curing agents are more preferred.
[0040] Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", and "SN375" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.
[0041] Specific examples of benzoxazine-based curing agents include "JBZ-OD100" (benzoxazine ring equivalent: 218), "JBZ-OP100D" (benzoxazine ring equivalent: 218), and "ODA-BOZ" (benzoxazine ring equivalent: 218) manufactured by JFE Chemical Corporation; "Pd" (benzoxazine ring equivalent: 217) and "Fa" (benzoxazine ring equivalent: 217) manufactured by Shikoku Chemical Industry Co., Ltd.; and "HFB2006M" (benzoxazine ring equivalent: 432) manufactured by Showa Polymer Co., Ltd.
[0042] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolac type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer), all of which are manufactured by Lonza Japan.
[0043] Specific examples of carbodiimide-based curing agents include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 262), V-07 (carbodiimide group equivalent: 200); V-09 (carbodiimide group equivalent: 200), all manufactured by Nisshinbo Chemical Inc.; and Stavaxol (registered trademark) P (carbodiimide group equivalent: 302), all manufactured by Rhein Chemie.
[0044] The amine-based curing agent may be a curing agent having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propanediamine, and the like. bis(4-aminophenyl)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 may be a commercially available product, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.
[0045] The ratio of the amount of the epoxy resin (A) to the curing agent (B) is preferably 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 in the epoxy resin] to [total number of reactive groups in the curing agent]. Here, the reactive group in the curing agent is an active hydroxyl group or the like, and varies depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is the value obtained by dividing the solid content mass of each curing agent by the reactive group ...
[0046] From the viewpoint of significantly obtaining the desired effects of the present invention, the content of the (B) curing agent is preferably 1 mass % or more, more preferably 2 mass % or more, and even more preferably 3 mass % or more, relative to 100 mass % of the non-volatile components in the resin composition, and is preferably 10 mass % or less, more preferably 8 mass % or less, and even more preferably 5 mass % or less.
[0047] <(C) Inorganic filler> The resin composition contains an inorganic filler (C) as component (C). By using the inorganic filler (C), the linear thermal expansion coefficient of the cured product of the resin composition can be reduced.
[0048] 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. Among these, calcium carbonate and silica are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, as the silica, spherical silica is preferred. The (C) inorganic filler may be used alone or in combination of two or more kinds.
[0049] Examples of commercially available products of component (C) include "ST7030-20" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "MSS-6" and "AC-5V" manufactured by Tatsumori Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30", "SFP-130MC", "FB-7SDC", "FB-5SDC", and "FB-3SDC" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; and "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", and "FE9" manufactured by Admatechs Co., Ltd.
[0050] The specific surface area of component (C) is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 / g or more. There is no particular upper limit, but it is preferably 60m2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area is determined by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.
[0051] From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle size of component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less.
[0052] The average particle size of component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter is used as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture by ultrasonic waves for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device with blue and red light wavelengths as the light source, and the particle size distribution of component (A) on a volume basis is measured using a flow cell method, and the average particle size can be calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.
[0053] From the viewpoint of improving moisture resistance and dispersibility, the (C) component is preferably treated with a surface treatment agent. Examples of the surface treatment agent include vinylsilane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane, organosilazane compounds, and titanate coupling agents. Among them, from the viewpoint of obtaining the effects of the present invention remarkably, vinylsilane coupling agents, (meth)acrylic coupling agents, aminosilane coupling agents, epoxysilane coupling agents, and silane coupling agents are preferred, and aminosilane coupling agents, epoxysilane coupling agents, and silane coupling agents are more preferred. In addition, the surface treatment agent may be used alone or in any combination of two or more types.
[0054] Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd.'s "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM503" (3-methacryloxypropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), ... Examples of such silane coupling agents include Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).
[0055] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. 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 0.2 parts by mass to 3 parts by mass, and even more preferably 0.3 parts by mass to 2 parts by mass.
[0056] 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 set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is more preferable that the content is 1 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:
[0057] The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. The carbon analyzer that can be used is the "EMIA-320V" manufactured by Horiba, Ltd.
[0058] From the viewpoint of effectively lowering the linear thermal expansion coefficient of the resin composition, the content (mass%) of the (C) component is preferably 80 mass% or more, more preferably 83 mass% or more, even more preferably 85 mass% or more, and preferably 95 mass% or less, more preferably 93 mass% or less, and even more preferably 90 mass% or less, when the nonvolatile components in the resin composition are taken as 100 mass%. In the present invention, even if a large amount of inorganic filler is contained in the resin composition, it is possible to maintain adhesion after the HAST test, so that it is possible to achieve both a reduction in the thermal expansion coefficient and an improvement in adhesion with the conductor layer after the HAST test.
[0059] <(D) Curing accelerator> The resin composition may contain (D) a curing accelerator as an optional component. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. The amine-based curing accelerators and imidazole-based curing accelerators are preferred, and the amine-based curing accelerators are more preferred. The curing accelerators may be used alone or in combination of two or more.
[0060] Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.
[0061] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.
[0062] Examples of the imidazole curing accelerator 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-furan Examples of the imidazole compounds include imidazole compounds such as 2-ethyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.
[0063] As the imidazole-based curing accelerator, a commercially available product may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation.
[0064] Examples of the guanidine curing accelerator 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, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of such biguanide include o-[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, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.
[0065] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
[0066] The content of the (C) curing accelerator, when the non-volatile components in the resin composition are taken as 100 mass%, is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, and particularly preferably 0.05 mass% or more, and is preferably 3 mass% or less, more preferably 1 mass% or less, and particularly preferably 0.5 mass% or less.
[0067] <(E) Other Additives> The resin composition may further contain other additives as optional components in addition to the above-mentioned components. Examples of such additives include resin additives such as thermoplastic resins, flame retardants, organic fillers, organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, thickeners, defoamers, leveling agents, adhesion promoters, colorants, and pigments. These additives may be used alone or in combination of two or more at any ratio.
[0068] Examples of colorants and pigments include fine particles of melamine, organic bentonite, etc.; phthalocyanine blue; phthalocyanine green; iodine green; diazo yellow; crystal violet; titanium oxide; carbon black such as "MA-600MJ-S" manufactured by Mitsubishi Chemical Corporation; and naphthalene black.
[0069] The content of the colorant or pigment, when the non-volatile components in the resin composition are taken as 100% by mass, is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, and is preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.
[0070] The above-mentioned resin composition may contain a solvent as necessary, but is preferably a solvent-free resin composition that does not substantially contain a solvent. Even if it does not contain a solvent, the resin composition can be fluidized when molded using 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 solvent" means, for example, that the content of the solvent is 1% by mass or less relative to the entire solvent-free resin composition.
[0071] <Method of producing resin composition> The resin composition of the present invention can be produced, for example, by a method of stirring the blending 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 in the epoxy resin (A), before producing the resin composition. In addition, it is preferable to remove impurities contained in the components (B) to (E) as necessary.
[0072] <Characteristics and properties of resin composition> The resin composition of the present invention may be liquid or solid, but is preferably liquid when molded. For example, a resin composition that is liquid at room temperature (e.g., 20°C) may be molded by compression molding at room temperature without any particular temperature adjustment, or may be heated to an appropriate temperature and molded by compression molding. A resin composition that is liquid at room temperature may be filled into a cartridge, the resin composition may be discharged from the cartridge, and then molded by compression molding. A resin composition that is solid at room temperature can usually be made liquid by adjusting its temperature to a higher temperature (e.g., 130°C), so that molding by compression molding can be performed by appropriate temperature adjustment such as heating. The resin composition can usually be made liquid at an appropriate temperature even without containing a solvent, and can be used, for example, as a liquid sealing material.
[0073] Here, the term "liquid" refers to a resin composition having a minimum melt viscosity of 4000 poise or less. The minimum melt viscosity of the resin composition is preferably 4000 Pa·s or less, more preferably 3000 poise or less, and even more preferably 2000 poise or less, and is preferably 50 poise or more, more preferably 60 poise or more, and even more preferably 70 poise or more. Here, the term "minimum melt viscosity" refers to the minimum melt viscosity at 60°C to 200°C. The minimum melt viscosity can be measured using a dynamic viscoelasticity measuring device. The minimum melt viscosity can be measured according to the method described in the examples below.
[0074] 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 thermal expansion coefficient. Therefore, the cured product provides a sealing layer or insulating layer with a low thermal expansion coefficient. The thermal expansion coefficient is preferably 15 ppm or less, more preferably 10 ppm or less, and even more preferably 9 ppm or less. On the other hand, the lower limit of the thermal expansion coefficient may be 1 ppm or more. The thermal expansion coefficient can be measured according to the method described in the examples below.
[0075] The cured product obtained by thermally curing the resin composition of the present invention at 180°C for 90 minutes exhibits a high shear strength with copper after the HAST test, and therefore exhibits excellent copper adhesion after the HAST test. Thus, the cured product provides a sealing layer or insulating layer that exhibits excellent copper adhesion after the HAST test. The shear strength after the HAST test is preferably 0.5 kgf / mm 2 More preferably, 0.6kgf / mm 2 More preferably, 0.7 kgf / mm 2 On the other hand, the upper limit of the shear strength is 10kgf / mm 2 The copper adhesion after the HAST test can be evaluated according to the method described in the examples below.
[0076] The amount of chloride ions in the resin composition of the present invention is 50 ppm or less, preferably 40 ppm or less, more preferably 30 ppm or less, 25 ppm or less. By setting the amount of chloride ions within this range, it is possible to obtain a cured product that has excellent adhesion to the conductor layer even after the HAST test. The lower limit of the amount of chloride ions is not particularly limited, but may be 0 ppm or more, 0.1 ppm or more, etc. The amount of chloride ions is measured in accordance with the sample combustion-ion chromatography method (BS EN 14582 2007).
[0077] Since the resin composition has the above-mentioned characteristics, it can be suitably used as a resin composition (resin composition for sealing) for sealing electronic devices such as organic EL devices and semiconductors, and in particular, it 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, the resin composition can be used as a resin composition for an insulating layer other than sealing. For example, the 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 a printed wiring board) (resin composition for insulating layer of circuit board).
[0078] 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.
[0079] The resin composition may also be used as an underfill material, for example, as a material for MUF (Molding Under Filling) that is used after a semiconductor chip is connected to a substrate.
[0080] Furthermore, the resin composition can be used in a wide range of applications in which resin compositions are used, such as resin sheets, sheet-like laminate materials such as prepregs, solder resists, die bonding materials, hole filling resins, and component embedding resins.
[0081] [Resin sheet] The resin sheet of the present invention has a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention and is usually formed of a resin composition.
[0082] From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, and even 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.
[0083] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.
[0084] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"); polycarbonate (hereinafter sometimes abbreviated as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); cyclic polyolefins; triacetyl cellulose (hereinafter sometimes abbreviated as "TAC"); polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; polyimide; and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.
[0085] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Among them, copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
[0086] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, an antistatic treatment or the like.
[0087] In addition, the support may be a support with a release layer having a release layer on the surface to be bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Examples of commercially available release agents include alkyd resin-based release agents such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation. Examples of the support with a release layer include "Lumirror T60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin Limited; and "Unipeel" manufactured by Unitika Limited.
[0088] The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the total thickness of the support with a release layer is preferably in the above range.
[0089] The resin sheet can be produced, for example, by applying the resin composition onto a support using a coating device such as a die coater. If necessary, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, and the resin sheet may be produced by applying the resin varnish. By using a solvent, the viscosity can be adjusted to improve the coatability. When the resin varnish is used, the resin varnish is usually dried after application to form a resin composition layer.
[0090] Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate ester 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 hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone; etc. The organic solvent may be used alone or in combination of two or more kinds at any ratio.
[0091] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.
[0092] The resin sheet may include any layer other than the support and the resin composition layer as necessary. For example, in the resin sheet, a protective film similar to that of the support may be provided on the surface of the resin composition layer not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent the adhesion of dirt and the like to the surface of the resin composition layer and scratches. 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 stored by being wound into a roll.
[0093] The resin sheet can be suitably used to form an insulating layer in the manufacture of a semiconductor chip package (resin sheet for insulating a semiconductor chip package). For example, the resin sheet can be used to form an insulating layer of a circuit board (resin sheet for insulating a circuit board). Examples of packages using such boards include FC-CSP, MIS-BGA packages, and ETS-BGA packages.
[0094] The resin sheet can also be suitably used to seal a semiconductor chip (semiconductor chip sealing resin sheet). Applicable semiconductor chip packages include, for example, fan-out type WLP, fan-in type WLP, fan-out type PLP, fan-in type PLP, etc.
[0095] The resin sheet may also be used as a material for the MUF that is used after the semiconductor chip is connected to the substrate.
[0096] Furthermore, the resin sheet can be used in a wide range of other applications requiring high insulation reliability, for example, the resin sheet can be suitably used to form an insulating layer of a circuit board such as a printed wiring board.
[0097] [Circuit board] The circuit board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention. The circuit board can be produced, for example, by a production method including the following steps (1) and (2). (1) A step of forming a resin composition layer on a substrate. (2) A step of thermally curing the resin composition layer to form an insulating layer.
[0098] In step (1), a substrate is prepared. Examples of the substrate include glass epoxy substrates, metal substrates (such as stainless steel and cold-rolled steel plate (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a metal layer such as copper foil on the surface as a part of the substrate. For example, a substrate having a first metal layer and a second metal layer that can be peeled off on both surfaces may be used. When such a substrate is used, a conductor layer as a wiring layer that can function as a circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. Examples of materials for the metal layer include copper foil, copper foil with a carrier, and materials for the conductor layer described later, and copper foil is preferred. In addition, a commercially available product can be used as the substrate having such a metal layer, and examples thereof include "Micro Thin", an ultra-thin copper foil with a carrier manufactured by Mitsui Mining & Smelting Co., Ltd.
[0099] A conductor layer may be formed on one or both surfaces of the substrate. In the following description, a member including a substrate and a conductor layer formed on the substrate surface may be referred to as a "substrate with wiring layer" as appropriate. Examples of the conductor material included in the conductor layer include materials including 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. The conductor material may be a single metal or an alloy. Examples of the alloy include alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning in the formation of the conductor layer, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and alloys of nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy as alloys; are preferred. Among these, the single metals chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver and copper; and nickel-chromium alloys; are more preferable, and the single metal copper is particularly preferable.
[0100] The conductor layer may be patterned, for example, to function as a wiring layer. In this case, the line (circuit width) / space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20 / 20 μm or less (i.e., pitch is 40 μm or less), more preferably 10 / 10 μm or less, even more preferably 5 / 5 μm or less, even more preferably 1 / 1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not need to be the same throughout the conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.
[0101] The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.
[0102] The conductor layer can be formed, for example, by a method including a step of laminating a dry film (photosensitive resist film) on a substrate, a step of forming a pattern by exposing and developing the dry film under predetermined conditions using a photomask to obtain a patterned dry film, a step of forming a conductor layer by a plating method such as electrolytic plating using the developed patterned dry film as a plating mask, and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. The lamination conditions 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 peeling off of the dry film can be carried out using, for example, an alkaline peeling solution such as a sodium hydroxide solution.
[0103] After preparing the substrate, a resin composition layer is formed on the substrate. When a conductor layer is formed on the surface of the substrate, the resin composition layer is preferably formed so that the conductor layer is embedded in the resin composition layer.
[0104] The resin composition layer is formed, for example, by laminating a resin sheet and a substrate. This lamination can be performed, for example, by bonding the resin sheet to the substrate from the support side under heat and pressure, thereby laminating the resin composition layer to the substrate. Examples of the member for heat-pressing the resin sheet to the substrate (hereinafter, sometimes referred to as a "heat-pressing member") include a heated metal plate (such as a SUS plate) or a metal roll (such as a SUS roll). It is preferable to press the heat-pressing member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the substrate, rather than directly pressing the resin sheet.
[0105] The lamination of the substrate and the resin sheet may be carried out, for example, by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa. The thermocompression 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 carried out under reduced pressure conditions of a pressure of 13hPa or less.
[0106] After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing the support side with a thermocompression member. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The lamination and smoothing treatment may be performed successively using a vacuum laminator.
[0107] The resin composition layer can be formed, for example, by compression molding. The specific operation of the compression molding method is, for example, to prepare an upper mold and a lower mold as molds. The resin composition is applied to the substrate. The substrate to which the resin composition has been applied is attached to the lower mold. Then, the upper mold and the lower mold are clamped, and heat and pressure are applied to the resin composition to perform compression molding.
[0108] A specific operation of the compression molding method may be, for example, as follows: An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed on the lower mold. A substrate is attached to the upper mold. Then, the upper mold and the lower mold are clamped together so that the resin composition placed on the lower mold is in contact with the substrate attached to the upper mold, and heat and pressure are applied to perform compression molding.
[0109] 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, preferably 80°C or higher, more preferably 100°C or higher, even more preferably 120°C or higher, and preferably 200°C or lower, more preferably 170°C or lower, and even more preferably 150°C or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, even more preferably 5 MPa or higher, preferably 50 MPa or lower, more preferably 30 MPa or lower, and even more preferably 20 MPa or lower. The cure time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, and especially preferably 20 minutes or less. Usually, the mold is removed after the formation of the resin composition layer. The mold may be removed before or after the resin composition layer is thermally cured.
[0110] After forming the resin composition layer on the substrate, the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C), 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).
[0111] Before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheating treatment at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of usually 50° C. or more and less than 120° C. (preferably 60° C. or more and 110° C. or less, more preferably 70° C. or more and 100° C. or less) for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).
[0112] In the manner described above, a circuit board having an insulating layer can be manufactured. The method for manufacturing a circuit board may further include any optional step. For example, when a circuit board is manufactured using a resin sheet, the manufacturing method of the circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled off before or after the resin composition layer is thermally cured.
[0113] The method for manufacturing a circuit board may include, for example, a step of polishing the surface of the insulating layer after forming the insulating layer. The polishing method is not particularly limited. For example, the surface of the insulating layer can be polished using a surface grinder.
[0114] The method for manufacturing a circuit board may include, for example, a step (3) of connecting the conductor layers between layers, that is, a step of drilling holes in the insulating layer. This allows holes such as via holes and through holes to be formed in the insulating layer. Examples of methods for forming via holes include laser irradiation, etching, and mechanical drilling. The dimensions and shape of the via holes may be appropriately determined depending on the design of the circuit board. In addition, in the step (3), the insulating layer may be polished or ground to perform the interlayer connection.
[0115] After the via holes are formed, it is preferable to carry out a step of removing smears in the via holes. This step is sometimes called a desmear step. For example, when the conductive layer is formed on the insulating layer by a plating step, the via holes may be subjected to a wet desmear process. When the conductive layer is formed on the insulating layer by a sputtering step, a dry desmear process such as a plasma treatment process may be carried out. Furthermore, the insulating layer may be roughened by the desmear process.
[0116] Furthermore, before forming the conductor layer on the insulating layer, the insulating layer may be subjected to a roughening treatment. This roughening treatment usually roughens the surface of the insulating layer including the inside of the via hole. The roughening treatment may be either a dry or wet roughening treatment. An example of the dry roughening treatment is a plasma treatment. An example of the wet roughening treatment is a method in which a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid are performed in this order.
[0117] After the via holes are formed, a conductor layer is formed on the insulating layer. By forming a conductor layer at the position where the via holes are formed, the newly formed conductor layer and the conductor layer on the surface of the substrate are electrically connected to each other, and interlayer connection is performed. Examples of methods for forming the conductor layer include plating, sputtering, and vapor deposition, and plating is preferred. In a preferred embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. In addition, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. In addition, this conductor layer may have a single layer structure, or may have a multi-layer structure including two or more layers of different types of materials.
[0118] Here, an example of an embodiment in which a conductor layer is formed on an insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern is formed on the formed plating seed layer, exposing a part of the plating seed layer corresponding to a desired wiring pattern. After forming an electrolytic plating layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by a process such as etching, and a conductor layer having a desired wiring pattern can be formed. Note that, when forming the conductor layer, the dry film used to form the mask pattern is the same as the above-mentioned dry film.
[0119] The method for producing 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 embedded in the insulating layer is obtained. This step (4) can be performed, for example, when a substrate having a peelable metal layer is used.
[0120] [Semiconductor chip package] The semiconductor chip package according to the first embodiment of the present invention includes the above-mentioned circuit board and a semiconductor chip mounted on the circuit board. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit board.
[0121] The bonding conditions between the circuit board and the semiconductor chip may be any conditions that allow conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, the conditions used in flip-chip mounting of the semiconductor chip may be used. Also, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.
[0122] An example of a bonding method is a method in which a semiconductor chip is pressure-bonded to a circuit board. Pressure-bonding conditions are a pressure-bonding temperature 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 a pressure-bonding time usually in the range of 1 second to 60 seconds (preferably in the range of 5 seconds to 30 seconds).
[0123] Another example of the bonding method is a method of bonding a semiconductor chip to a circuit board by reflow. The reflow conditions may be in the range of 120°C to 300°C.
[0124] After the semiconductor chip is bonded to the circuit board, the semiconductor chip may be filled with a molded underfill material. As the molded underfill material, the above-mentioned resin composition or the above-mentioned resin sheet may be used.
[0125] The semiconductor chip package according to the second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition that encapsulates the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition usually functions as an encapsulation layer. An example of the semiconductor chip package according to the second embodiment is a fan-out type WLP.
[0126] The manufacturing method of a semiconductor chip package such as a fan-out type WLP is as follows: (A) a step of laminating a temporary fixing film on a substrate; (B) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (C) a step of laminating a resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and thermally curing the composition to form an encapsulating layer; (D) peeling the substrate and the temporary fixing film from the semiconductor chip; (E) a step of forming a rewiring formation layer (insulating layer) on the surface from which the substrate and the temporary fixing film of the semiconductor chip have been peeled off; (F) forming a conductor layer (rewiring layer) on a rewiring formation layer (insulating layer); and (G) forming a solder resist layer on the conductor layer. The method for manufacturing a semiconductor chip package may also include (H) dicing the plurality of semiconductor chip packages into individual semiconductor chip packages.
[0127] For 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 contents of which are incorporated herein by reference.
[0128] A semiconductor chip package according to a third embodiment of the present invention is, for example, a semiconductor chip package according to the second embodiment, in which a rewiring formation layer or a solder resist layer is formed from a cured product of the resin composition of the present invention.
[0129] [Semiconductor Devices] Examples of semiconductor devices in which the above-mentioned semiconductor chip package is mounted include various semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.). EXAMPLES
[0130] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In the following description, the amounts of "ppm", "parts" and "%" are based on mass unless otherwise specified. Furthermore, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.
[0131] The epoxy resin used in the examples was a commercially available product that had been purified by distillation. The silica A, silica B, and silica C used in the examples and comparative examples are as follows: Silica A: average particle size 9.2 μm, specific surface area 3.3 m 2 / g, silica surface-treated with KBM573 (Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane). Silica B: average particle size 8.5μm, specific surface area 3.2m 2 / g, silica surface-treated with KBM403 (Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane). Silica C: average particle size 9.6μm, specific surface area 2.9m 2 / g, silica surface-treated with KBM4803 (long-chain epoxy-type silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.).
[0132] <Example 1> Five parts of a glycidylamine type epoxy resin (epoxy equivalent: 95 g / eq.), five parts of a bisphenol type epoxy resin (a 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent: 169 g / eq.), seven parts of an acid anhydride curing agent (manufactured by New Japan Chemical Co., Ltd., "MH-700", acid anhydride equivalent: 164 g / eq.), 140 parts of silica A, 0.1 parts of a curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ", 1-benzyl-2-phenylimidazole), and 0.6 parts of carbon black (manufactured by Mitsubishi Chemical Corporation, "MA-600MJ-S") were mixed and uniformly dispersed using a mixer to prepare resin composition 1.
[0133] <Example 2> In Example 1, silica A was changed to silica B. Resin composition 2 was prepared in the same manner as in Example 1 except for the above-mentioned points.
[0134] <Example 3> In Example 1, silica A was changed to silica C. Resin composition 3 was prepared in the same manner as in Example 1 except for the above-mentioned points.
[0135] <Example 4> In addition, 3 parts of an alicyclic epoxy resin (epoxy equivalent: 136 g / eq.) was used in Example 1. Resin composition 4 was prepared in the same manner as in Example 1 except for the above-mentioned points.
[0136] <Comparative Example 1> In Example 1, 5 parts of glycidylamine type epoxy resin (epoxy equivalent 95g / eq.) was replaced with 5 parts of glycidylamine type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent 95g / eq.), Five parts of bisphenol type epoxy resin (a 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent: 169 g / eq.) was changed to five parts of bisphenol F type epoxy (Nagase ChemteX Corporation, "EX-211", epoxy equivalent: 138 g / eq.). Except for the above, resin composition 5 was prepared in the same manner as in Example 1. In Comparative Example 1, "630" and "EX-211" were not distilled, and commercially available products were used as they were.
[0137] <Measurement of chloride ion amount> The amount of chloride ions in each of the resin compositions 1 to 5 produced in the examples and comparative examples was measured by combustion-ion chromatography (in accordance with BS EN 14582 2007).
[0138] <Measurement of coefficient of thermal expansion (CTE)> On the release-treated 12-inch silicon wafer, Resin Compositions 1 to 5 prepared in the examples and comparative examples were compression-molded using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure 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 release-treated silicon wafer and heated at 180°C for 90 minutes to thermally cure the resin composition layer to prepare a cured sample. The cured sample was cut into pieces with a width of 5 mm and a length of 15 mm to obtain test pieces. For these test pieces, thermomechanical analysis was performed by the tensile loading method using a thermomechanical analyzer (ThermoPlus TMA8310 manufactured by Rigaku Corporation). Specifically, after mounting the test piece on the thermomechanical analyzer, two consecutive measurements were performed under the measurement conditions of a load of 1 g and a heating rate of 5°C / min. Then, in the second measurement, the coefficient of thermal expansion (ppm / °C) in the planar direction in the range from 25°C to 150°C was calculated.
[0139] <Measurement of Minimum Melt Viscosity> The minimum melt viscosities of Resin Compositions 1 to 5 prepared in the examples and comparative examples were measured using a dynamic viscoelasticity measuring apparatus (Rheosol-G3000 manufactured by UBM). For 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was raised from the starting temperature of 60°C to 200°C at a heating rate of 5°C / min, and the dynamic viscoelastic modulus was measured under the measurement conditions of a measurement temperature interval of 2.5°C, a vibration of 1 Hz, and a strain of 1 deg to obtain the value of the minimum melt viscosity.
[0140] <Evaluation of Copper Adhesion after HAST Test> The resin compositions prepared in the Examples and Comparative Examples were formed on the copper surface of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") to a diameter of 4 mm and a height of 5 mm. Specifically, the resin composition was filled into a 5 mm-high cylinder using a silicon rubber frame hollowed out to a diameter of 4 mm, heated at 180°C for 90 minutes, and then the silicon rubber frame was removed to prepare a test piece. The test piece was subjected to a high temperature and high humidity environmental test (HAST) at 130°C, 85% RH, and 96 hours, and then the shear strength of the interface between the copper and the test piece was measured using a bond tester (Dage Series 4000) with the head position 1 mm from the substrate and the head speed of 700 μm / s. The test was performed five times, and the average value was used. The shear strength was 0.5 kgf / mm 2 If it is more than 0.5kgf / mm, mark it as "〇"; if it is more than 0.5kg 2 Those that were less than this were marked as "X".
[0141] [Table 1]
[0142] In Examples 1 to 4, it was confirmed that even when components (D) and (E) were not contained, the results were similar to those of the above Examples, although to a different extent.
Claims
1. (A) an epoxy resin, (B) a curing agent, and (C) containing an inorganic filler, A resin composition that is substantially free of solvent, The resin composition is a resin composition for an insulating layer that adheres to copper, A resin composition, in which the amount of chloride ions contained in the resin composition is 50 ppm or less, as measured in accordance with a sample combustion-ion chromatography method (BS EN 14582 2007).
2. (A) an epoxy resin, (B) a curing agent, and (C) a resin composition containing an inorganic filler, The resin composition is a resin composition for an insulating layer that adheres to copper, A resin composition having an amount of chloride ions contained in the resin composition of 50 ppm or less, as measured in accordance with a sample combustion-ion chromatography method (BS EN 14582 2007) (excluding epoxy resin compositions containing an epoxy resin represented by the following general formula (2) and a curing agent). 【Chemistry 1】 (In the formula, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y is a di(ethyleneoxy)ethyl group, a tri(ethyleneoxy)ethyl group, a tetra(ethyleneoxy)ethyl group, a propyleneoxypropyl group, a di(propyleneoxy)propyl group, a tri(propyleneoxy)propyl group, a poly(propyleneoxy)propyl group, a butyleneoxybutyl group, a di(butyleneoxy)butyl group, a tri(butyleneoxy)butyl group, a tetra(butyleneoxy)butyl group, an alkylene group having 4 to 15 carbon atoms, or an aliphatic hydrocarbon group having a cycloalkane skeleton and having 6 to 17 carbon atoms.)
3. The resin composition according to claim 1 or 2, wherein the component (A) consists essentially of at least one selected from the group consisting of bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, alicyclic epoxy resins, naphthylene ether type epoxy resins, and tetraphenylethane type epoxy resins.
4. (A) an epoxy resin, (B) a curing agent, and (C) a resin composition containing an inorganic filler, The resin composition is a resin composition for an insulating layer that adheres to copper, The component (A) contains a glycidyl amine type epoxy resin, A resin composition, in which the amount of chloride ions contained in the resin composition is 50 ppm or less, as measured in accordance with a sample combustion-ion chromatography method (BS EN 14582 2007).
5. A resin composition according to any one of claims 1 to 4, wherein component (A) comprises a distilled epoxy resin.
6. The resin composition according to any one of claims 1 to 5, wherein the content of the component (C) is 80 mass% or more, when the non-volatile components in the resin composition are 100 mass%.
7. The resin composition according to any one of claims 1 to 6, wherein the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes has a thermal expansion coefficient of 15 ppm / °C or less.
8. The resin composition according to any one of claims 1 to 7, wherein the component (B) comprises an acid anhydride-based curing agent.
9. The resin composition according to any one of claims 1 to 8, wherein the resin composition is liquid.
10. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 9.
11. A semiconductor chip package comprising: the circuit board according to claim 10; and a semiconductor chip mounted on the circuit board.
12. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 9 that encapsulates the semiconductor chip.