Resin composition

Abstract

The present invention provides a resin composition that can obtain a cured product having high joint strength and suppressed warpage, a resin sheet using the resin composition, a circuit substrate, and a semiconductor chip package. The present invention is a resin composition comprising: (A) an epoxy resin, (B) at least one curing agent selected from an acid anhydride-based curing agent, an amine-based curing agent, and a phenol-based curing agent, (C) a polyester polyol resin having an aromatic structure, and (D) an inorganic filler, wherein the content of the (C) component is 2 mass% or more and 20 mass% or less, based on 100 mass% of the non-volatile content of the resin composition.

Description

Technical Field

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

[0002] In recent years, the demand for small, high-performance electronic devices such as smartphones and tablets has increased, and with it, the demand for insulating materials used as sealing layers and insulating layers in these small electronic devices has also increased. Known examples of such insulating materials include those described in Patent Documents 1 and 2.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2019 / 044803

[0006] Patent document 2: International Publication No. 2019 / 131413. Summary of the Invention

[0007] Technical problem to be solved by the invention

[0008] In recent years, demand for smaller electronic devices has led to a demand for thinner insulating layers and sealing layers used in these devices. Thinning insulating layers and sealing layers tend to cause warping, so there is a demand for insulating layers and sealing layers that can suppress warping. Furthermore, insulating layers and sealing layers are also desired to have high bonding strength with other layers.

[0009] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a resin composition that can produce a cured product having high bonding strength and suppressed warpage, and a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.

[0010] Technical solutions used to solve technical problems

[0011] The present inventors have conducted intensive research to address the aforementioned issues and have discovered that a resin composition comprising (A) an epoxy resin, (B) at least one curing agent selected from an acid anhydride curing agent, an amine curing agent, and a phenolic curing agent, (C) a predetermined amount of a polyester polyol resin having an aromatic structure, and (D) an inorganic filler can solve the aforementioned issues, thereby completing the present invention. Specifically, the present invention encompasses the following aspects:

[0012] [1] A resin composition comprising:

[0013] (A) Epoxy resin,

[0014] (B) at least one curing agent selected from anhydride curing agents, amine curing agents and phenol curing agents,

[0015] (C) a polyester polyol resin having an aromatic structure, and

[0016] (D) inorganic filler materials,

[0017] When the non-volatile component in the resin composition is set to 100% by mass, the content of the component (C) is 2% by mass or more and 20% by mass or less;

[0018] [2] The resin composition according to [1], wherein the component (A) comprises a fused ring skeleton;

[0019] [3] The resin composition according to [1] or [2], wherein the terminal of component (C) is either a hydroxyl group or a carboxyl group;

[0020] [4] The resin composition according to any one of [1] to [3], wherein the content of the component (D) is 60% by mass or more and 95% by mass or less, based on 100% by mass of the non-volatile component in the resin composition;

[0021] [5] The resin composition according to any one of [1] to [4], wherein the component (C) is a resin having a structure derived from polyester and a structure derived from polyol;

[0022] [6] The resin composition according to [5], wherein the structure derived from the polyol includes any of an ethylene oxide structure, a propylene oxide structure, and a butylene oxide structure;

[0023] [7] The resin composition according to any one of [1] to [6], wherein the component (C) has a bisphenol skeleton;

[0024] [8] The resin composition according to any one of [1] to [7], wherein, when c1 is the content of the component (C) when the non-volatile components in the resin composition are 100% by mass, and d1 is the content of the component (D) when the non-volatile components in the resin composition are 100% by mass, d1 / c1 is 5 or more and 70 or less;

[0025] [9] The resin composition according to any one of [1] to [8], which is used for a sealing layer;

[0026]

[10] A resin sheet comprising: a support; and a resin composition layer provided on the support and comprising the resin composition described in any one of [1] to [9];

[0027]

[11] A circuit board comprising: an insulating layer formed from a cured product of the resin composition described in any one of [1] to [9];

[0028]

[12] A semiconductor chip package comprising: the circuit substrate described in

[11] , and a semiconductor chip mounted on the circuit substrate;

[0029]

[13] A semiconductor chip package comprising: a semiconductor chip sealed with the resin composition according to any one of [1] to [9] or the resin sheet according to

[10] .

[0030] Effects of the Invention

[0031] According to the present invention, it is possible to provide a resin composition that can provide a cured product having high bonding strength and suppressed warpage, and a resin sheet, a circuit board, and a semiconductor chip package using the resin composition. DETAILED DESCRIPTION

[0032] The present invention will be described in detail below with reference to the embodiments and examples. However, the present invention is not limited to the embodiments and examples given below, and can be implemented with any modifications without departing from the scope of the claims and their equivalents.

[0033] [Resin composition]

[0034] The resin composition of the present invention comprises (A) an epoxy resin, (B) at least one curing agent selected from an anhydride curing agent, an amine curing agent and a phenolic curing agent, (C) a polyester polyol resin with an aromatic structure, and (D) an inorganic filler. When the non-volatile component in the resin composition is set to 100% by mass, the content of the (C) component is 2% by mass or more and 20% by mass or less. By using such a resin composition, a cured product with high bonding strength and suppressed warping can be obtained. In addition, in the present invention, a cured product with a low coefficient of thermal expansion (CTE) can also be obtained.

[0035] The cured product of the resin composition can be preferably used as an insulating layer or a sealing layer of a circuit board or a semiconductor chip package, utilizing its excellent properties, and can be particularly preferably used as a sealing layer.

[0036] The resin composition may further contain any components in addition to components (A) to (D). Examples of such optional components include (E) a curing accelerator, (F) a solvent, and (F) other additives. The following describes each component of the resin composition in detail.

[0037] <(A) Epoxy resin>

[0038] As the (A) component, the resin composition contains an (A) epoxy resin. As the (A) epoxy resin, for example, a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a phenol novolac type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, a alicyclic epoxy resin, a heterocyclic type epoxy resin, an epoxy resin containing a spiro ring, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin, a tetraphenyl ethane type epoxy resin, a naphthalene ether type epoxy resin, a t-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a naphthol novolac type epoxy resin, and the like epoxy resins containing a condensed ring skeleton can be given. The epoxy resin can be used alone or in combination of two or more. Among them, as the (A) epoxy resin, it is preferable to include an epoxy resin containing a condensed ring skeleton from the viewpoint of obtaining the effects of the present application significantly.

[0039] As the (A) epoxy resin, it is preferable that the resin composition contains an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining the desired effects of the present application significantly, 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, relative to 100% by mass of the non-volatile components of the (A) epoxy resin.

[0040] The epoxy resin includes an epoxy resin that is in a liquid state at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is in a solid state at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resin"). As the (A) epoxy resin, the resin composition can contain only a liquid epoxy resin, only a solid epoxy resin, or preferably a combination of a liquid epoxy resin and a solid epoxy resin, but from the viewpoint of obtaining the effects of the present application significantly, it is preferable to contain only a liquid epoxy resin.

[0041] As the liquid epoxy resin, it is preferable that the liquid epoxy resin has two or more epoxy groups in one molecule.

[0042] As liquid epoxy resins, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, and more preferred are alicyclic epoxy resins having an ester skeleton and naphthalene type epoxy resins.

[0043] Specific examples of liquid epoxy resins include: "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, "828US", "jER828EL", "825", and "EPIKOTE 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "630" and "630LSD" (glycidylamine-type epoxy resins) 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 Corporation, and Nagase Examples include "EX-721" (glycidyl ester epoxy resin) manufactured by ChemteX Corporation, "CELLOXIDE 2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation, "PB-3600" (epoxy resin with a butadiene structure) manufactured by Daicel Corporation, and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane epoxy resins) manufactured by Nippon Steel & Sumitomo Metal Chemicals Corporation. These resins may be used alone or in combination.

[0044] The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0045] As solid epoxy resins, preferred are biphenylol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and more preferred are naphthalene-type epoxy resins.

[0046] 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 resin) 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-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" (naphthylene ether type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "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" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. ”, “NC3000”, “NC3000L”, “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 Corporation, “YX4000HK” (dimethylphenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation ester), "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "PG-100" and "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, and "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These resins may be used alone or in combination of two or more.

[0047] As (A) epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, their amount ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20 by mass ratio, more preferably 1:1 to 1:10, and particularly preferably 1:1.5 to 1:5. By making the amount ratio of liquid epoxy resin and solid epoxy resin within the described range, the desired effect of the present invention can be significantly obtained. In addition, when usually used in the form of a resin sheet, appropriate adhesion is brought. In addition, when usually used in the form of a resin sheet, sufficient flexibility can be obtained and handleability is improved. In addition, a cured product with sufficient breaking strength can usually be obtained.

[0048] The epoxy equivalent weight of the epoxy resin (A) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. By setting the epoxy equivalent weight within this range, the cured product of the resin composition layer has a sufficient crosslinking density, resulting in an insulating layer with reduced surface roughness. The epoxy equivalent weight is the mass of the epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent weight can be measured in accordance with JIS K7236.

[0049] From the viewpoint of significantly achieving the desired effects of the present invention, the weight average molecular weight (Mw) of the epoxy resin (A) is preferably from 100 to 5000, more preferably from 100 to 4000, and even more preferably from 200 to 5000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0050] When the non-volatile component in resin combination is set to 100 mass %, from the viewpoint of the insulating layer obtaining good mechanical strength, insulation reliability, the content of (A) epoxy resin is preferably more than 1 mass %, more preferably more than 2 mass %, further more preferably more than 3 mass %.From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit of the content of epoxy resin is preferably below 30 mass %, more preferably below 25 mass %, especially preferably below 20 mass %.It should be noted that in the present invention, as long as not otherwise expressly stated, the content of each component in resin combination is the value when the non-volatile component in resin combination is set to 100 mass %.

[0051] <(B) At least one curing agent selected from anhydride curing agents, amine curing agents, and phenol curing agents>

[0052] The resin composition contains, as component (B), at least one curing agent selected from the group consisting of anhydride curing agents, amine curing agents, and phenolic curing agents. Curing agents generally react with component (A) to cure the resin composition. In particular, by including these curing agents in the resin composition, in addition to curing the resin composition by reacting with component (A), a cured product with suppressed warping can be obtained. Component (B) may be used alone or in combination of two or more.

[0053] Examples of the acid anhydride curing agent include curing agents 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, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, homodimethyl phthalic anhydride, ... Polymer-type acid anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 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-furyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), and styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid.

[0054] As the acid anhydride curing agent, a commercially available product can be used, and examples thereof include "MH-700" manufactured by Shin Nippon Chemical Co., Ltd.

[0055] As the amine curing agent, there can be mentioned a curing agent having one or more amino groups in one molecule, and for example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc. can be mentioned, wherein, from the viewpoint of exerting the desired effect of the present invention, aromatic amines are preferred. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. As specific examples of the amine curing agent, there can be mentioned: 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, metaphenylenediamine, 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.

[0056] Amine curing agents that can be used are commercially available products, and examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "EPICURE W" manufactured by Mitsubishi Chemical Corporation.

[0057] As phenolic curing agents, curing agents having more than one, preferably more than two, hydroxyl groups bonded to aromatic rings (phenyl rings, naphthalene rings, etc.) in one molecule can be enumerated. Among them, compounds having hydroxyl groups bonded to a benzene ring are preferably used. In addition, from the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferably used. In addition, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferably used, and phenolic curing agents containing a triazine skeleton are more preferably used. From the viewpoint of highly satisfying heat resistance, water resistance and adhesion, particularly preferably a novolac curing agent containing a triazine skeleton is used.

[0058] Specific examples of phenolic curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemicals Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", and "KA-1165" manufactured by DIC Corporation; "GDP-6115L", "GDP-6115H", and "ELPC75" manufactured by Gunei Chemical Co., Ltd.; and "2,2-diallylbisphenol A" manufactured by Sigma-Aldrich.

[0059] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, the content of component (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less.

[0060] When the number of epoxy groups of (A) component is set to 1, the number of active groups of (B) component is preferably more than 0.1, more preferably more than 0.3, further more preferably more than 0.5, preferably less than 2, more preferably less than 1.8, further more preferably less than 1.5.Herein, " the number of epoxy groups of (A) component " refers to the value obtained by adding up the mass of the non-volatile components of (A) component present in the resin combination divided by the value obtained by the epoxy equivalent. In addition, " the number of active groups of (B) component " refers to the value obtained by adding up the mass of the non-volatile components of (B) component present in the resin combination divided by the value obtained by the active group equivalent. By making the number of active groups of (B) component when the number of epoxy groups of (A) component is set to 1 within the range, the desired effect of the present invention can be significantly obtained.

[0061] <(C) Polyester polyol resin having an aromatic structure>

[0062] The resin composition contains a polyester polyol resin (C) having an aromatic structure as component (C). By including component (C) in the resin composition, stress in the cured product is relaxed, resulting in a cured product having high bonding strength and suppressed warping. Furthermore, because component (C) acts to relax stress, the coefficient of thermal expansion (CTE) of the cured product is generally reduced. Components (C) may be used alone or in combination of two or more.

[0063] As the content of (C) component, from the viewpoint of obtaining the cured product with high bond strength and the generation of warping being suppressed, when the non-volatile component in the resin combination is made into 100 mass %, be more than 2 mass %, preferably more than 3 mass %, more preferably more than 4 mass %, further more preferably more than 5 mass %.From the viewpoint of obtaining the cured product of excellent bond strength and thermal expansion coefficient, the upper limit is below 20 mass %, preferably below 15 mass %, more preferably below 10 mass %, further more preferably below 8 mass %.

[0064] From the viewpoint of suppressing the occurrence of curing of the cured product, improving the adhesion to the conductor layer such as copper foil, and then improving the hydrolyzability, (C) component is preferably a resin having a structure derived from polyester and a structure derived from polyol. This resin can be obtained by, for example, reacting polyol with polycarboxylic acid. In addition, as (C) component, it is preferably to have an aromatic structure in any structure of the structure derived from polyester and the structure derived from polyol. From the viewpoint of significantly obtaining the effect of the present invention, it is more preferably to have a bisphenol skeleton in any structure of the structure derived from polyester and the structure derived from polyol, and further preferably to have a bisphenol skeleton in the structure derived from polyol. Aromatic structure refers to a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. As the bisphenol skeleton, for example, bisphenol A skeleton, bisphenol B skeleton, bisphenol C skeleton, bisphenol AF skeleton, etc. can be cited, and it is preferably a bisphenol A skeleton.

[0065] (C) component, from the viewpoint of improving compatibility with (A) epoxy resin and adhesion with copper foil etc., it is preferred that the molecular chain terminal of this (C) component is any of hydroxyl group and carboxyl group. As the number of hydroxyl group and carboxyl group contained in (C) component, on average per molecule, it is preferred that 2 or more, preferably 6 or less, more preferably 4 or less, further more preferably 3 or less, particularly preferably 2.

[0066] From the viewpoint of significantly achieving the effects of the present invention, the structure derived from the polyol preferably has an alkylene oxide structure having 2 or more carbon atoms, such as an ethylene oxide structure (-CH2CH2O-), a propylene oxide structure (-CH2CH2CH2O-), or a butylene oxide structure (-CH2CH2CH2CH2O-).

[0067] Examples of polyols include aliphatic polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butanediol; polyols with an alicyclic structure such as cyclohexanedimethanol; polyols with an aromatic structure such as bisphenol A and bisphenol F; and polyols obtained by modifying these polyols with an aromatic structure with an alkylene oxide. Among these polyols, preferred are polyols with an alicyclic structure, polyols with an aromatic structure, and polyols obtained by modifying these polyols with an alkylene oxide. More preferred are polyols obtained by modifying these polyols with an aromatic structure with an alkylene oxide. These polyols may be used alone or in combination.

[0068] Examples of the alkylene oxide used for modifying the polyol having an aromatic structure include alkylene oxides having 2 or more carbon atoms, such as ethylene oxide, propylene oxide, and butylene oxide. The upper limit of the carbon number of the alkylene oxide having 2 or more carbon atoms is preferably 4 or less, more preferably 3 or less.

[0069] The number average molecular weight of the polyol is preferably at least 50 and is preferably at most 1500, more preferably at most 1000, further preferably at most 700.

[0070] Commercially available polyols may be used, and examples of commercially available polyols include "Hyprox MDB-561" manufactured by DIC Corporation.

[0071] Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid; and anhydrides and esters thereof.

[0072] Polycarboxylic acid can use 1 kind alone, also can use in combination more than 2 kinds, as polycarboxylic acid, preferably comprises aliphatic polycarboxylic acid.As the containing ratio of aliphatic polycarboxylic acid, in the total content of polycarboxylic acid, preferably more than 5 mol %, more preferably more than 10 mol %, preferably below 100 mol %.

[0073] As the polybasic acid, an aliphatic polybasic acid and an aromatic polybasic acid are used in combination as one embodiment. The content ratio of the aromatic polybasic acid and the aliphatic polybasic acid (aromatic polybasic acid / aliphatic polybasic acid) is preferably 1 / 99 or more, more preferably 30 / 70 or more, further more preferably 50 / 50 or more, preferably 99 / 1 or less, more preferably 90 / 10 or less, further more preferably 85 / 15 or less, on a molar basis. By setting the content ratio of the aromatic polybasic acid and the aliphatic polybasic acid within the above range, the effect of the present application can be significantly obtained.

[0074] As the (C) component, an oxyalkylene unit having 4 or more carbon atoms can be contained, to the extent that does not hinder the object of the present application. The content of the oxyalkylene unit having 4 or more carbon atoms is preferably 10% by mass or less, more preferably 5% by mass or less, further more preferably 3% by mass or less, particularly preferably 1% by mass or less.

[0075] As the (C) component, it can be produced, for example, by reacting a polyol with a polybasic acid. The reaction temperature is preferably 190°C or more, more preferably 200°C or more, preferably 250°C or less, more preferably 240°C or less. Further, the reaction time is preferably 1 hour or more, preferably 100 hours or less.

[0076] At the time of the reaction, a catalyst can be used as necessary. As the catalyst, for example, a titanium-based catalyst such as tetraisopropyl titanate, tetrabutyl titanate, a tin-based catalyst such as dibutyltin oxide, an organic sulfonic acid-based catalyst such as p-toluenesulfonic acid, and the like can be given. The catalyst can be used alone or two or more kinds can be used in combination.

[0077] The content of the catalyst is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, relative to 100 parts by mass of the total of the polyol and the polybasic acid, from the viewpoint of efficiently performing the reaction.

[0078] The hydroxyl value of the (C) component is preferably 2 mgKOH / g or more, more preferably 4 mgKOH / g or more, further more preferably 6 mgKOH / g or more, 10 mgKOH / g or more, 25 mgKOH / g or more, 30 mgKOH / g or more, or 35 mgKOH / g or more, and is preferably 450 mgKOH / g or less, more preferably 100 mgKOH / g or less, further more preferably 50 mgKOH / g or less, 45 mgKOH / g or less, or 40 mgKOH / g or less, from the viewpoint of significantly obtaining the effect of the present application. The hydroxyl value can be measured by a method based on JIS K0070.

[0079] Furthermore, the acid value of the component (C) is preferably 2 mgKOH / g or more, more preferably 4 mgKOH / g or more, further preferably 6 mgKOH / g or more, 10 mgKOH / g or more, 25 mgKOH / g or more, 30 mgKOH / g or more, or 35 mgKOH / g or more, and is preferably 450 mgKOH / g or less, more preferably 100 mgKOH / g or less, further more preferably 50 mgKOH / g or less, 45 mgKOH / g or less, or 40 mgKOH / g or less, from the viewpoint of significantly achieving the effects of the present invention. The acid value can be measured by a method in accordance with JIS K0070.

[0080] The viscosity of component (C) at 75°C is preferably 0.1 Pa·s or more, more preferably 0.2 Pa·s or more, further preferably 0.5 Pa·s or more, and is preferably 25 Pa·s or less, more preferably 20 Pa·s or less, further preferably 15 Pa·s or less, from the viewpoint of significantly achieving the effects of the present invention. The viscosity can be measured using, for example, an E-type viscometer.

[0081] The number average molecular weight of the component (C) is preferably 500 or more, more preferably 1000 or more, further preferably 1500 or more, 2000 or more, or 2500 or more, from the viewpoint of improving compatibility with the epoxy resin (A) and adhesion to copper foil, etc., and is preferably 7000 or less, more preferably 6000 or less, further more preferably 5000 or less. The number average molecular weight can be measured by GPC (gel permeation chromatography).

[0082] The glass transition temperature of the component (C) is preferably -100°C or higher, more preferably -80°C or higher, further preferably -70°C or higher, and is preferably 50°C or lower, more preferably 40°C or lower, further preferably 30°C or lower, from the viewpoint of significantly achieving the effects of the present invention. The glass transition temperature is a value measured by DSC (differential scanning calorimetry).

[0083] <(D) Inorganic fillers>

[0084] The resin composition contains (D) an inorganic filler. By containing (D) an inorganic filler in the resin composition, a cured product having an excellent thermal expansion coefficient can be obtained.

[0085] 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, calcium zirconate, zirconium phosphate, and zirconium tungstic phosphotungstate. Among them, silica and alumina are preferred, and silica is particularly preferred. As silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be mentioned. In addition, spherical silica is preferred as silica. (D) The inorganic filler can be used alone or in combination of two or more.

[0086] Examples of commercially available inorganic fillers (D) include: "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C," "YA050C," "YA050C-MJE," and "YA010C" manufactured by Admatechs Corporation; "UFP-30" manufactured by Denka Corporation; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; and "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Admatechs Corporation.

[0087] From the viewpoint of significantly achieving the desired effects of the present invention, the average particle size of the inorganic filler (D) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 25 μm or less, more preferably 5 μm or less, further preferably 1 μm or less.

[0088] (D) The average particle size of the inorganic filler can be measured using a laser diffraction scattering method based on Mie scattering theory. Specifically, it can be measured in the following manner: using a laser diffraction scattering particle size distribution measuring device, the particle size distribution of the inorganic filler is made on a volume basis, and the median particle size is used as the average particle size. The sample can be measured using a sample obtained by the following method: 100 mg of inorganic filler and 10 g of methyl ethyl ketone are weighed into a vial and dispersed for 10 minutes using ultrasound. For the sample, a laser diffraction particle size distribution measuring device is used, the wavelength of the light source is set to blue and red, and the particle size distribution of the volume basis of the inorganic filler (D) is measured in a flow cell manner, and the average particle size is calculated from the obtained particle size distribution as the median particle size. As a laser diffraction particle size distribution measuring device, for example, "LA-960" manufactured by Horiba, Ltd. can be cited.

[0089] From the viewpoint of significantly obtaining the desired effects of the present invention, the specific surface area of ​​the inorganic filler (D) is preferably 1 m 2 / g or more, preferably 1.5 m 2 / g or more, particularly preferably 2 m 2 / g or above or 3 m 2 There is no particular upper limit, but it is preferably 60 m 2 / g or less, 50 m 2 / g or less than 40 m 2 The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area by the BET multipoint method.

[0090] From the viewpoint of improving moisture resistance and dispersibility, the (D) inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. The surface treatment agent may be used alone or in any combination of two or more.

[0091] Examples of commercially available surface treatment agents include “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., and “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0092] From the viewpoint that the dispersibility of inorganic filler improves, the degree of surface treatment carried out by surface treatment agent is preferably controlled within a prescribed range. Specifically, 100 parts by mass of inorganic filler is preferably surface treated by 0.2 to 5 parts by mass of surface treatment agent, preferably surface treated by 0.2 to 3 parts by mass of surface treatment agent, preferably surface treated by 0.3 to 2 parts by mass of surface treatment agent.

[0093] The degree of surface treatment by 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 More than 0.1 mg / m 2 More than 0.2 mg / m 2 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, 1 mg / m 2 Below, preferably 0.8 mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0094] The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added as a solvent to the inorganic filler surface-treated by 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 amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0095] From the viewpoint of significantly achieving the effects of the present invention, the content of the inorganic filler (D) is preferably 60% by mass or more, more preferably 65% ​​by mass or more, further preferably 70% by mass or more and 75% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, further preferably 92% by mass or less and 90% by mass or less, based on the non-volatile component in the resin composition being 100% by mass.

[0096] When the content of the component (D) when the non-volatile component in the resin composition is 100% by mass is set to d1, and the content of the component (C) when the non-volatile component in the resin composition is 100% by mass is set to c1, from the viewpoint of significantly obtaining the effects of the present invention, d1 / c1 is preferably 5 or more, more preferably 10 or more, further preferably 15 or more, preferably 70 or less, more preferably 60 or less, further preferably 50 or less, 45 or less, 40 or less, or 35 or less.

[0097] <(E) Curing accelerator>

[0098] In addition to the above-mentioned components, the resin composition may further contain (E) a curing accelerator as an optional component. By containing (E) a curing accelerator, the curing time and the like can be effectively adjusted.

[0099] Examples of curing accelerators include phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, and metal curing accelerators. Among these, phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metal curing accelerators are preferred, and amine curing accelerators, imidazole curing accelerators, and metal curing accelerators are more preferred. One curing accelerator may be used alone, or two or more may be used in combination.

[0100] 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, and butyltriphenylphosphonium thiocyanate. Triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

[0101] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, 1,8-diazabicyclo[5.4.0]undecene-7,4-dimethylaminopyridine, and 2,4,6-tris(dimethylaminomethyl)phenol. 4-Dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]undecene are preferred.

[0102] As the imidazole-based curing accelerator, for example, 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-methyl-5-hydroxymethylimidazole, 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 the like imidazole compounds, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole.

[0103] As the imidazole-based curing accelerator, commercially available products can be used, and for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation, "Curezol 2MZ", "2E4MZ", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "Cl1Z-A", "2MZ-OK", "2MA-OK", "2PHZ" and the like manufactured by Shikoku Chemicals Corporation can be mentioned.

[0104] 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, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. Preferred examples include dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0105] As metal curing accelerators, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be mentioned. Specific examples of organometallic complexes include organocobalt complexes such as cobalt acetylacetonate (II) and cobalt acetylacetonate (III), organocopper complexes such as copper acetylacetonate (II), organozinc complexes such as zinc acetylacetonate (II), organoferric complexes such as iron acetylacetonate (III), organonickel complexes such as nickel acetylacetonate (II), and organomanganese complexes such as manganese acetylacetonate (II). As organometallic salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate can be mentioned.

[0106] From the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile component in the resin composition is 100% by mass, the content of the (E) curing accelerator is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, further preferably at least 0.1% by mass, preferably at most 1.5% by mass, more preferably at most 1% by mass, further more preferably at most 0.5% by mass.

[0107] <(F)Solvent>

[0108] The resin composition may further contain any solvent as a volatile component. Examples of the solvent include organic solvents. In addition, one solvent may be used alone, or two or more solvents may be used in combination in any proportion. The smaller the amount of solvent, the better. Relative to 100% by mass of the non-volatile component in the resin composition, the amount of the solvent is preferably 3% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, further preferably 0.1% by mass or less, further preferably 0.01% by mass or less, and particularly preferably no solvent (0% by mass). In addition, when the amount of solvent is small as described above, the resin composition may be in a paste state. The viscosity of the paste-like resin composition at 25°C is preferably in the range of 20 Pa･s to 1000 Pa･s.

[0109] <(G) Other additives>

[0110] In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include thermoplastic resins, curing agents other than component (B), organic fillers, thickeners, defoamers, leveling agents, adhesion-imparting agents, flame retardants, and other resin additives. These additives may be used alone or in combination of two or more.

[0111] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a solvent or the like is added to the components as needed, and the mixture is mixed and dispersed using a rotary mixer or the like.

[0112] <Physical Properties and Applications of Resin Compositions>

[0113] The cured product obtained by heat curing the resin composition at 180°C for 90 minutes exhibits excellent bonding strength. Bonding strength can be expressed, for example, by shear strength. Therefore, the cured product generally provides an insulating layer or sealing layer with excellent shear strength. As a shear strength, 2 kgf / mm is preferred. 2 The shear strength can be measured by the method described in the examples below.

[0114] A cured product obtained by heat-curing a resin composition at 190°C for 90 minutes generally exhibits a low coefficient of thermal expansion (CTE). Consequently, such a cured product provides an insulating layer or sealant layer with a low coefficient of thermal expansion. The coefficient of thermal expansion (CTE) is preferably less than 13 ppm / °C. The coefficient of thermal expansion can be measured using the method described in the Examples below.

[0115] The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes shows the characteristic that the warping amount is suppressed. Therefore, the cured product provides an insulating layer or a sealing layer with suppressed warping amount. Specifically, the resin composition is compression-molded on a silicon wafer to obtain a resin composition layer. A sample substrate is obtained by thermally curing the resin composition layer. Using a Shadow Moire measuring device, the warping amount of the sample substrate at 25°C is determined in accordance with JEITA EDX-7311-24 of the Electronics and Information Technology Industries Association standard. The warping amount is less than 2 mm. The warping amount can be specifically measured according to the method described in the embodiments described later.

[0116] The resin composition has the above-mentioned characteristics and can be suitably used as a resin composition for sealing electronic devices such as organic EL devices or semiconductors (resin composition for sealing), and can be particularly 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 sealing purposes, the resin composition can also be used as a resin composition for insulating purposes for an insulating layer. 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 an insulating layer of a semiconductor chip package) and a resin composition for forming an insulating layer of a circuit substrate (including a printed wiring board) (resin composition for an insulating layer of a circuit substrate).

[0117] Examples of semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out WLP (Wafer Level Package), fan-in WLP, fan-out PLP (Panel Level Package), and fan-in PLP.

[0118] Furthermore, the resin composition can be used as an underfill material, for example, a MUF (Molding Under Filling) material used after a semiconductor chip is connected to a substrate.

[0119] Furthermore, the resin composition can be used in a wide range of applications where a resin composition can be used, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, die bonding materials, hole-filling resins, and component embedding resins.

[0120] [Resin sheet]

[0121] The resin sheet of the present invention comprises 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 the resin composition.

[0122] From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, further 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 for example, it can be 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0123] Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0124] When a film formed of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"); polycarbonate (hereinafter sometimes referred to as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes referred to as "PMMA"); cyclic polyolefins; triacetyl cellulose (hereinafter sometimes referred to as "TAC"); polyether sulfide (hereinafter sometimes referred to as "PES"); polyether ketone; polyimide; and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0125] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil. Among them, copper foil is preferred. The copper foil may be a foil made of copper alone or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0126] The support may be subjected to treatment such as matte treatment, corona treatment, and antistatic treatment on the surface thereof that contacts the resin composition layer.

[0127] In addition, as a support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used in the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins can be mentioned. As commercially available release agents, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Co., Ltd., which are alkyd resin release agents, can be mentioned. In addition, as a support with a release layer, for example, "Lumirror T60" manufactured by Toray Industries, Ltd.; "Purex" manufactured by Teijin Limited; "Unipeel" manufactured by UNITIKA Co., Ltd.; and the like can be mentioned.

[0128] 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 thickness of the entire support with a release layer is preferably within the above range.

[0129] Resin sheet can for example be coated on support and manufacture by using coating devices such as die coaters (die coater).In addition, as required, resin composition can also be dissolved in an organic solvent and made into resin varnish, be coated with this resin varnish and manufacture resin sheet.By using a solvent, viscosity can be adjusted so that coating property is improved.Use in the situation of resin varnish, usually make resin varnish dry after coating, form resin composition layer.

[0130] Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve 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; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more in any ratio.

[0131] Drying can be carried out by known methods such as heating and blowing hot air. Regarding drying conditions, drying is performed so that the content of the organic solvent in the resin composition layer is generally 10% by mass or less, preferably 5% by mass or less. Drying conditions also vary depending on the boiling point of the organic solvent in the resin varnish. For example, when using a resin varnish containing 30% to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0132] The resin sheet may include 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 bonded to the support (i.e., the surface on the opposite side of the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can be used to prevent the surface of the resin composition layer from being attached to garbage or being damaged. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, the resin sheet can be rolled up and stored.

[0133] Resin sheets can be suitably used to form insulating layers in the manufacture of semiconductor chip packages (insulating resin sheets for semiconductor chip packages). For example, resin sheets can be used to form insulating layers for circuit boards (insulating resin sheets for circuit boards). Examples of packages using such substrates include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

[0134] Furthermore, the resin sheet can be suitably used for sealing semiconductor chips (resin sheet for semiconductor chip sealing). Examples of applicable semiconductor chip packages include fan-out WLP, fan-in WLP, fan-out PLP, and fan-in PLP.

[0135] Furthermore, the resin sheet can also be used as a material for MUF used after the semiconductor chip is connected to the substrate.

[0136] 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.

[0137] [Circuit board]

[0138] The circuit substrate of the present invention includes a cured product layer formed from a cured product of the resin composition of the present invention. The cured product layer may serve as an insulating layer or a sealing layer. The circuit substrate may be manufactured, for example, by a manufacturing method comprising the following steps (1) and (2):

[0139] (1) forming a resin composition layer on a substrate;

[0140] (2) A step of thermally curing the resin composition layer to form an insulating layer.

[0141] In step (1), a substrate is prepared. As the substrate, for example, a glass epoxy substrate, a metal substrate (stainless steel, cold-rolled steel sheet (SPCC) etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate etc. can be cited. In addition, as a part of the substrate, a metal layer such as copper foil can be provided on the surface. For example, a substrate having a first metal layer and a second metal layer that can be peeled off on both surfaces can be used. When such a substrate is used, usually, a conductor layer that can function as a wiring layer for circuit wiring is formed on the surface of the second metal layer opposite to the first metal layer. As the material of the metal layer, copper foil, copper foil with a carrier, the material of the conductor layer described later, etc. can be cited, preferably copper foil. In addition, as such a substrate having a metal layer, a commercially available product can be used, and for example, an ultra-thin copper foil "Micro Thin" with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd. can be cited.

[0142] In addition, a conductor layer can be formed on one or both surfaces of the substrate. In the following description, a member comprising a substrate and a conductor layer formed on the surface of the substrate is sometimes appropriately referred to as a "substrate with a wiring layer". As the conductor material contained in the conductor layer, for example, a material containing one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium can be mentioned. As the conductor material, a single metal can be used, or an alloy can be used. As the alloy, for example, an alloy of two or more metals selected from the above metals (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be mentioned. Among them, from the perspective of versatility, cost and ease of patterning of the conductor layer formation, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal; and an alloy of nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy as an alloy are preferred. Among them, single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloy, especially single metal of copper are more preferred.

[0143] For the conductor layer, for example, in order to make it function as a wiring layer, pattern processing can be performed. At this time, the ratio of the line width (circuit width) / line spacing (width between circuits) 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, further preferably 1 / 1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The spacing does not need to be the same over the entire conductor layer. The minimum spacing of the conductor layer can be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

[0144] 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.

[0145] The conductor layer can be formed, for example, by a method comprising the following steps: laminating a dry film (photosensitive resist) on a substrate; exposing and developing the dry film under predetermined conditions using a photomask to form a pattern, thereby obtaining a patterned dry film; forming a conductor layer by a plating method such as electroplating using the developed patterned dry film as a plating mask; and stripping the patterned dry film. A photosensitive dry film formed from a photoresist composition can be used as the dry film, for example, a dry film formed from a resin such as a novolac resin or an acrylic resin. The conditions for laminating the substrate and the dry film can be the same as the conditions for laminating the substrate and the resin sheet described below. For example, stripping the dry film can be performed using an alkaline stripping solution such as a sodium hydroxide solution.

[0146] After preparing a 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.

[0147] The formation of the resin composition layer can be carried out by, for example, stacking a resin sheet with a base material. About this stacking, for example, by heating and pressing the resin sheet on the base material from the support body side, so that the resin composition layer is attached to the base material and carried out. As a member (hereinafter sometimes referred to as "heating and pressing member") for heating and pressing the resin sheet on the base material, for example, a heated metal plate (SUS end plate etc.) or a metal roller (SUS roller etc.) etc. can be enumerated. It should be noted that it is better not to directly press the heating and pressing member onto the resin sheet, but to press it across an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface unevenness of the base material.

[0148] The lamination of the substrate and the resin sheet can be implemented, for example, by a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa. The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably implemented under reduced pressure conditions with a pressure of 13hPa or less.

[0149] After lamination, the laminated resin sheets can be smoothed by applying pressure under normal pressure (atmospheric pressure), for example, by applying a heat-pressing member from the support side. The smoothing pressing conditions can be the same as those for the heat-pressing lamination described above. Lamination and smoothing can be performed continuously using a vacuum laminator.

[0150] The resin composition layer can be formed, for example, by compression molding. Specifically, the compression molding method includes preparing an upper mold and a lower mold as molds. The resin composition is applied to a substrate. The substrate coated with the resin composition is mounted on the lower mold. The upper and lower molds are then clamped together, and heat and pressure are applied to the resin composition to perform compression molding.

[0151] 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, a base material is installed in the upper mold. Then, the upper mold and the lower mold are clamped in a manner such that the resin composition placed on the lower mold and the base material installed in the upper mold are in contact, and heat and pressure are applied to perform compression molding.

[0152] 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 exert excellent compression moldability, for example, preferably 80°C or more, more preferably 100°C or more, further preferably 120°C or more, preferably 200°C or less, more preferably 170°C or less, further preferably 150°C or less. In addition, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, further preferably 5 MPa or more, preferably 50 MPa or less, more preferably 30 MPa or less, further preferably 20 MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, and particularly preferably 20 minutes or less. Typically, after the resin composition layer is formed, the mold is removed. The removal of the mold can be performed before or after thermal curing of the resin composition layer.

[0153] After forming a resin composition layer on a substrate, the resin composition layer is thermally cured to form an insulating layer. Thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but the curing temperature is generally in the range of 120°C to 240°C (preferably 150°C to 220°C, more preferably 170°C to 200°C), and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

[0154] Before thermally curing the resin composition layer, the resin composition layer may be subjected to a preheating treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin composition layer may 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 to 150 minutes, more preferably 15 to 120 minutes).

[0155] By performing the above operation, a circuit substrate having an insulating layer can be manufactured. In addition, the method for manufacturing a circuit substrate may further include any steps. For example, when a resin sheet is used to manufacture the circuit substrate, the method for manufacturing the circuit substrate may include a step of peeling off the support of the resin sheet. The support may be peeled off before or after the thermal curing of the resin composition layer.

[0156] The method for manufacturing a circuit board may include, for example, a step of grinding the surface of the insulating layer after forming the insulating layer. The grinding method is not particularly limited. For example, the surface of the insulating layer may be ground using a surface grinder.

[0157] The method for manufacturing a circuit substrate may include, for example, step (3) of making interlayer connections between the conductor layers, i.e., a step of forming holes in the insulating layer. Thus, holes such as through holes and vias can be formed in the insulating layer. Examples of methods for forming through holes include laser irradiation, etching, and mechanical drilling. The size and shape of the through holes can be appropriately determined based on the design of the circuit substrate. It should be noted that step (3) may be performed by grinding or polishing the insulating layer to make interlayer connections.

[0158] After the through-hole is formed, it is preferred to perform a process for removing contaminants from the through-hole. This process is sometimes referred to as a desmear process. For example, when the conductive layer is formed on the insulating layer by a plating process, the through-hole may be subjected to a wet desmear process. Alternatively, when the conductive layer is formed on the insulating layer by a sputtering process, a dry desmear process such as a plasma treatment process may be performed. Furthermore, the desmear process may be used to roughen the insulating layer.

[0159] Furthermore, the insulating layer may be subjected to a roughening treatment before forming the conductive layer thereon. This roughening treatment typically roughens the surface of the insulating layer, including the interior of the through-holes. The roughening treatment may be either dry or wet. Examples of dry roughening treatments include plasma treatment. Examples of wet roughening treatments include a method in which swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution are sequentially performed.

[0160] After the through-hole is formed, a conductor layer can be formed on the insulating layer. By forming a conductor layer at the position where the through-hole is formed, the newly formed conductor layer is connected to the conductor layer on the surface of the substrate, and interlayer connection can be performed. Regarding the method for forming the conductor layer, for example, plating method, sputtering method, evaporation method, etc. can be cited, among which plating method is preferred. In a preferred embodiment, the surface of the insulating layer is plated using an appropriate method such as a semi-additive method and a full-additive method to form a conductor layer with a desired wiring pattern. In addition, when the support body 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 conductor layer formed can be a single metal or an alloy. In addition, the conductor layer can have a single-layer structure or a multilayer structure including two or more layers of different types of materials.

[0161] Here, an example of an embodiment of forming a conductor layer on an insulating layer is described in detail. A plating seed layer (seed layer) is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, corresponding to the desired wiring pattern, to expose a portion of the plating seed layer. On the exposed plating seed layer, an electrolytic plating layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or other processes, thereby forming a conductor layer with a desired wiring pattern. 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.

[0162] 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 conductive layer embedded in the insulating layer can be obtained. This step (4) can be performed, for example, when a substrate having a removable metal layer is used.

[0163] [Semiconductor chip packaging]

[0164] A semiconductor chip package according to a first embodiment of the present invention includes the above-mentioned circuit substrate and a semiconductor chip mounted on the circuit substrate. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit substrate.

[0165] The bonding conditions between the circuit substrate and the semiconductor chip can be any conditions that allow for conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit substrate. For example, the conditions used in flip-chip mounting of semiconductor chips can be used. Alternatively, for example, the semiconductor chip and the circuit substrate can be bonded via an insulating adhesive.

[0166] As an example of a joining method, a method of pressing a semiconductor chip to a circuit substrate can be cited. As pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, 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 in the range of 5 seconds to 30 seconds).

[0167] Another example of the bonding method is a method of bonding a semiconductor chip to a circuit board by reflow soldering. The reflow soldering conditions can be set within a range of 120°C to 300°C.

[0168] After the semiconductor chip is bonded to the circuit board, the semiconductor chip can be filled with a mold underfill material. As the mold underfill material, the resin composition described above can be used, or the resin composition layer of the resin sheet described above can also be used.

[0169] A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor chip and a cured product of the aforementioned resin composition that seals the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition typically functions as a sealing layer. Examples of the semiconductor chip package according to the second embodiment include fan-out WLPs.

[0170] The manufacturing method of a semiconductor chip package such as a fan-out WLP includes the following steps:

[0171] (A) a step of laminating a temporary fixing film on a substrate;

[0172] (B) a step of temporarily fixing the semiconductor chip on a temporary fixing film;

[0173] (C) laminating the 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 it to form a sealing layer;

[0174] (D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;

[0175] (E) forming a rewiring forming layer (insulating layer) on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled off;

[0176] (F) forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer); and

[0177] (G) forming a solder resist layer on the conductor layer. In addition, the method for manufacturing a semiconductor chip package may include the following steps:

[0178] (H) A step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them.

[0179] For details of the method for manufacturing such a semiconductor chip package, reference may be made to paragraphs 0066 to 0081 of International Publication No. 2016 / 035577, the contents of which are incorporated herein by reference.

[0180] The semiconductor chip package according to the third embodiment of the present invention is, for example, a semiconductor chip package according to the second embodiment in which a redistribution layer or a solder resist layer is formed from a cured product of the resin composition of the present invention.

[0181] [Semiconductor devices]

[0182] Examples of semiconductor devices equipped with the above-mentioned semiconductor chip package include various semiconductor devices for electrical products (such as computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and aircraft). Example

[0183] The present invention is described in detail below with reference to the following examples. However, the present invention is not limited to the following examples. In the following description, unless otherwise specified, "parts" and "%" indicating quantities refer to "parts by mass" and "mass %," respectively. Furthermore, unless otherwise specified, the operations described below are performed under normal temperature and pressure.

[0184] In addition, silica A, silica B, and alumina A used in Examples and Comparative Examples are as follows:

[0185] Silica A: average particle size 1.8 μm, specific surface area 3.5 m 2 / g, silica surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.);

[0186] Silica B: average particle size 3.2 μm, specific surface area 4.6 m 2 / g, silica surface-treated with 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.);

[0187] Alumina: average particle size 6.2 μm, specific surface area 1.7 m 2 / g of aluminum oxide surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.).

[0188] <Synthesis Example 1: Synthesis of Polyester Polyol Resin A Having an Aromatic Structure>

[0189] 779.1 parts by mass of bisphenol A glycol ether (Hyprox MDB-561, manufactured by DIC Corporation), 132.9 parts by mass of isophthalic acid, and 40.4 parts by mass of sebacic acid were added to a reactor, and heating and stirring were initiated. Subsequently, after the internal temperature was raised to 230°C, 0.10 parts by mass of tetraisopropyl titanate was added, and the mixture was reacted at 230°C for 24 hours to synthesize a polyester polyol resin A having an aromatic structure. The resulting polyester polyol resin A having an aromatic structure had OH groups at both terminals, a hydroxyl value of 36.9 mgKOH / g, a number average molecular weight of 3040, a glass transition temperature of -14°C, and a viscosity of 9 Pa·s at 75°C.

[0190] <Synthesis Example 2: Synthesis of Polyester Polyol Resin B Having an Aromatic Structure>

[0191] 596.8 parts by mass of bisphenol A glycol ether (Hyprox MDB-561, manufactured by DIC Corporation) and 257.4 parts by mass of sebacic acid were added to a reactor, and heating and stirring were initiated. Subsequently, the internal temperature was raised to 230°C, and 0.10 parts by mass of tetraisopropyl titanate was added. The reaction was continued at 230°C for 24 hours to synthesize a polyester polyol resin B having an aromatic structure. The resulting polyester polyol resin B had -COOH groups at both ends, a hydroxyl value of 36.6 mgKOH / g, a number average molecular weight of 3070, a glass transition temperature of -33°C, and a viscosity of 12 Pa·s at 75°C.

[0192] <Example 1>

[0193] 6.6 parts of an alicyclic epoxy resin (manufactured by Daicel Corporation, “CEL2021P”, epoxy equivalent 136 g / eq.), 8 parts of a naphthalene-type epoxy resin (manufactured by DIC Corporation, “HP4032D”, epoxy equivalent 142 g / eq.), 0.5 parts of an amine curing agent (manufactured by Nippon Kayaku Co., Ltd., “KAYAHARD AA”), 2.5 parts of the polyester polyol resin A having an aromatic structure synthesized in Synthesis Example 1, 80 parts of silica A, and 0.4 parts of a curing accelerator (manufactured by Shikoku Chemicals Co., Ltd., “2MA-OK”) were uniformly dispersed in a mixer to obtain a resin composition 1.

[0194] <Example 2>

[0195] In Example 1, 0.5 parts of the polyester polyol resin A having an aromatic structure was replaced with 0.5 parts of the polyester polyol resin B having an aromatic structure. A resin composition 2 was prepared in the same manner as in Example 1 except for the above matters.

[0196] <Example 3>

[0197] 3 parts of an alicyclic epoxy resin (manufactured by Daicel Corporation, “CEL2021P”, epoxy equivalent 136 g / eq.), 3 parts of a naphthalene-type epoxy resin (manufactured by DIC Corporation, “HP4032D”, epoxy equivalent 142 g / eq.), 10 parts of an acid anhydride curing agent (manufactured by Shin Nippon Chemical Co., Ltd., “MH-700”), 4 parts of the polyester polyol resin A having an aromatic structure synthesized in Synthesis Example 1, 100 parts of silica A, and 0.5 parts of a curing accelerator (manufactured by Shikoku Chemicals Co., Ltd., “2MA-OK”) were uniformly dispersed in a mixer to obtain resin composition 3.

[0198] <Example 4>

[0199] In Example 3, 4 parts of polyester polyol resin A having an aromatic structure was replaced with 8 parts of polyester polyol resin B having an aromatic structure, and 100 parts of silica A was replaced with 130 parts of alumina A. Resin composition 4 was prepared in the same manner as in Example 3 except for the above matters.

[0200] <Example 5>

[0201] 7 parts of an alicyclic epoxy resin (manufactured by Daicel Corporation, “CEL2021P”, epoxy equivalent 136 g / eq.), 8 parts of a naphthalene-type epoxy resin (manufactured by DIC Corporation, “HP4032D”, epoxy equivalent 142 g / eq.), 1 part of a phenolic curing agent (2,2-diallylbisphenol A), 2 parts of the polyester polyol resin A having an aromatic structure synthesized in Synthesis Example 1, 70 parts of silica A, and 0.4 parts of a curing accelerator (manufactured by Shikoku Chemicals Co., Ltd., “2MA-OK”) were uniformly dispersed in a mixer to obtain a resin composition 5.

[0202] Comparative Example 1

[0203] In Example 2, 2.5 parts of the polyester polyol resin A having an aromatic structure was not used. Except for the above matters, a resin composition 6 was prepared in the same manner as in Example 2.

[0204] Comparative Example 2

[0205] In Example 3, the amount of the polyester polyol resin A having an aromatic structure was changed from 4 parts to 0.5 parts. A resin composition 7 was prepared in the same manner as in Example 3 except for the above matters.

[0206] Comparative Example 3

[0207] In Example 3, the amount of the polyester polyol resin A having an aromatic structure was changed from 4 parts to 35 parts. A resin composition 8 was prepared in the same manner as in Example 3 except for the above matters.

[0208] <Evaluation of shear strength>

[0209] On a polyimide-coated silicon wafer, a resin composition 1 to 8 produced in the examples and comparative examples was filled into a cylindrical shape of 5 mm in height using a silicone rubber frame having a diameter of 4 mm excavated. After heating at 180°C for 90 minutes, a test piece formed of a cured product of the resin composition was produced by removing the silicone rubber frame. The shear strength of the interface between the polyimide and the test piece was measured using a bond tester (manufactured by Dage Corporation, Series 4000) under conditions where the head position was 1 mm from the substrate and the head speed was 700 μm / s. The test was performed five times, and the average value thereof was used to evaluate according to the following criteria;

[0210] O: 2 kgf / mm 2 the above case

[0211] X: less than 2 kgf / mm 2 the case.

[0212] <Measurement of warpage amount>

[0213] On a 12-inch silicon wafer, a resin composition produced in the examples and comparative examples was compression-molded using a compression molding device (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes) to form a resin composition layer having a thickness of 300 μm. Then, the resin composition layer was heat-cured at 180°C for 90 minutes. Thus, a test substrate including a silicon wafer and a cured product layer of the resin composition was obtained. The warpage amount at 25°C was measured for the test substrate using an image moire measuring device (Thermoire AXP manufactured by Akorometrix Corporation). The measurement was performed according to JEITA EDX-7311-24 of the Electronic Information Technology Industry Association. Specifically, a fitting plane obtained by the least squares method for all data of the substrate surface of the measurement region was used as a reference surface, and the difference between the minimum value and the maximum value in the perpendicular direction from the reference surface was obtained as the warpage amount. The warpage amount of less than 2 mm was evaluated as "O", and the warpage amount of 2 mm or more was evaluated as "X".

[0214] <Measurement of coefficient of thermal expansion (CTE)>

[0215] On a 12-inch silicon wafer subjected to a mold release treatment, the resin compositions 1 to 8 produced 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 having a thickness of 300 μm. Then, the resin composition layer was peeled from the silicon wafer subjected to the mold release treatment, and the resin composition layer was cured by heating at 180°C for 90 minutes to produce a cured product sample. The cured product sample was cut into a test piece having a width of 5 mm and a length of 15 mm. For the test piece, thermal mechanical analysis was performed by a tensile load method using a thermal mechanical analysis device ("ThermoPlus TMA8310" manufactured by Rigaku Kikai K.K.). Specifically, after the test piece was loaded into the thermal mechanical analysis device, two measurements were continuously performed under measurement conditions of a load of 1 g and a temperature increase rate of 5°C / minute. Thus, in the second measurement, the coefficient of thermal expansion in the planar direction (ppm / °C) in the range from 25°C to 150°C was calculated, and evaluation was performed in accordance with the following criteria;

[0216] O: a case where it is lower than 13 ppm / °C

[0217] X: a case where it is 13 ppm / °C or more.

[0218] [Table 1]

[0219] .

[0220] It was confirmed that in Examples 1 to 5, even in the case where the (E) component was not contained, although the degree was different, the same results as in the above examples were obtained.

Claims

1. A resin composition comprising the following components (A) to (D): (A) Epoxy resin, (B) at least one curing agent selected from anhydride curing agents, amine curing agents and phenol curing agents, (C) a polyester polyol resin having an aromatic structure, and (D) inorganic filler materials, in, Component (A) comprises a cycloaliphatic epoxy resin, Component (C) has a bisphenol skeleton, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 1% by mass or more and 30% by mass or less. When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 2% by mass or more and 20% by mass or less. When the nonvolatile matter in the resin composition is 100 mass %, content of the component (D) is 60 mass % or more and 95 mass % or less.

2. The resin composition according to claim 1, wherein The component (A) contains a fused ring skeleton.

3. The resin composition according to claim 1, wherein The terminal of the component (C) is either a hydroxyl group or a carboxyl group.

4. The resin composition according to claim 1, wherein The acid value of the component (C) is 25 mgKOH / g or more.

5. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 3% by mass or more. The resin composition according to claim 1 , wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 20% by mass or less.

7. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 0.1% by mass or more.

8. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 0.3% by mass or more.

9. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 20% by mass or less.

10. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 10% by mass or less.

11. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 5% by mass or more.

12. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 8% by mass or less.

13. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 75% by mass or more.

14. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 90% by mass or less.

15. The resin composition according to claim 1, wherein The component (C) is a resin having a structure derived from polyester and a structure derived from polyol.

16. The resin composition according to claim 15, wherein The structure derived from the polyol includes any of an ethylene oxide structure, a propylene oxide structure, and a butylene oxide structure.

17. The resin composition according to claim 1, wherein When c1 represents the content of the component (C) when the nonvolatile component in the resin composition is 100% by mass, and d1 represents the content of the component (D) when the nonvolatile component in the resin composition is 100% by mass, d1 / c1 is 5 or more and 70 or less.

18. The resin composition according to claim 1, wherein When c1 represents the content of the component (C) when the nonvolatile component in the resin composition is 100% by mass, and d1 represents the content of the component (D) when the nonvolatile component in the resin composition is 100% by mass, d1 / c1 is 15 or more.

19. The resin composition according to claim 1, wherein When c1 represents the content of the component (C) when the nonvolatile component in the resin composition is 100% by mass, and d1 represents the content of the component (D) when the nonvolatile component in the resin composition is 100% by mass, d1 / c1 is 35 or less.

20. The resin composition according to claim 1, which is used for a sealing layer.

21. A resin sheet comprising: Support body, and A resin composition layer provided on the support and comprising the resin composition according to any one of claims 1 to 20. 22 . A circuit board comprising a cured product layer formed from a cured product of the resin composition according to claim 1 .

23. A semiconductor chip package, comprising: The circuit substrate according to claim 22, and A semiconductor chip is mounted on the circuit substrate. 24 . A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to claim 1 or the resin sheet according to claim 21 .