TWI896781B - Resin composition - Google Patents

Abstract

The present invention is to provide a resin composition, etc., that can produce a cured product with high bonding strength to other layers, a low linear thermal expansion coefficient, and suppressed warping and flow marks. The present invention provides a solution to this problem in 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 phenol curing agent, (C) a polyester polyol resin having an aliphatic structure, and (D) an inorganic filler. The content of component (C) is 1% by mass or greater and 20% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

Description

Resin composition

The present invention relates to a resin composition and, moreover, to a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device obtained using the resin composition.

In recent years, demand for compact, high-performance electronic devices such as smartphones and tablets has increased, and with it, the insulating materials used to package semiconductor chips in these compact electronic devices are also required to have higher functionality. Such insulating layers are known to be formed by curing a resin composition (see, for example, Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2017-008312

[The problem that the invention aims to solve]

When using insulating materials for sealing applications, it is desirable to suppress warping and flow marks in the cured product. Furthermore, the sealing layer should have high bonding strength with other layers and a low coefficient of linear thermal expansion (CTE).

The present invention is to provide a resin composition that provides a cured product with high bonding strength to other layers, a low linear thermal expansion coefficient, and suppressed warping and flow marks; and a resin sheet, circuit board, semiconductor chip package, and semiconductor device using the resin composition. [Means for Solving the Problem]

The inventors of the present invention have diligently examined the above-mentioned issues and have found that the above-mentioned issues can be solved by including an epoxy resin, a specific hardener, a specific amount of a polyester polyol resin having an aliphatic structure, and an inorganic filler in the resin composition, thereby finally completing the present invention.

That is, the present invention includes the following contents. [1] A resin composition comprising: (A) an epoxy resin, (B) at least one curing agent selected from an anhydride curing agent, an amine curing agent, and a phenol curing agent, (C) a polyester polyol resin having an aliphatic structure, and (D) an inorganic filler; wherein, when the non-volatile components in the resin composition are taken as 100% by mass, the content of component (C) is 1% by mass or more and 20% by mass or less. [2] The resin composition as described in [1], wherein component (A) comprises a condensed ring skeleton. [3] The resin composition as described in [1] or [2], wherein the terminal of component (C) is either a hydroxyl group or a carboxyl group. [4] The resin composition according to any one of [1] to [3], wherein the component (C) is a resin having a structure derived from polyester and a structure derived from polyol. [5] The resin composition according to [4], wherein the structure derived from polyol includes any one of an ethylene oxide structure, a propylene oxide structure, and a butylene oxide structure. [6] The resin composition according to any one of [1] to [5], wherein the content of the component (D) is 60% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. [7] The resin composition according to any one of [1] to [6], which is for use as a sealant. [8] A resin sheet comprising a support and a resin composition layer comprising the resin composition described in any one of [1] to [7] and disposed on the support. [9] A circuit substrate comprising a hardened layer formed by hardening the resin composition described in any one of [1] to [7]. [10] A semiconductor chip package comprising the circuit substrate described in [9] and a semiconductor chip mounted on the circuit substrate. [11] A semiconductor chip package comprising a semiconductor chip sealed by the resin composition described in any one of [1] to [7] or the resin sheet described in [8]. [12] A semiconductor device comprising the semiconductor chip package as described in [10] or [11]. [Effects of the invention]

The present invention provides a resin composition that can produce a cured product having high bonding strength with other layers, a low linear thermal expansion coefficient, and suppressed warping and flow marks; and a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device using the resin composition.

[Form of implementing the invention]

The present invention is described in detail below with reference to suitable embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the patent application and its equivalents.

[Resin Composition] The resin composition comprises (A) an epoxy resin, (B) at least one curing agent selected from an anhydride-based curing agent, an amine-based curing agent, and a phenol-based curing agent, (C) a polyester polyol resin having an aliphatic structure, and (D) an inorganic filler. The content of component (C) is 1% by mass to 20% by mass, based on 100% by mass of the non-volatile components in the resin composition. This resin composition provides a cured product with high bond strength to other layers, a low coefficient of linear thermal expansion, and suppressed warping and flow marks.

The resin composition may further include optional components in combination with components (A) to (D). Examples of optional components include (E) a curing accelerator and (F) other additives. The following describes each component of the resin composition in detail.

<(A) Epoxy Resin> The resin composition contains (A) epoxy resin as component (A). Examples of the epoxy resin (A) include bixylene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butylcatechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, and glycidylamine. Type epoxy resins, epoxy propyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins with a butadiene structure, aliphatic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, oxalic acid type epoxy resins, oxalic acid dimethanol type epoxy resins, naphthyl ether type epoxy resins, trihydroxymethyl type epoxy resins, tetraphenylethane type epoxy resins, epoxy propyl ether type epoxy resins, etc. Among these, component (A) is preferably one or more selected from naphthalene-type epoxy resins, aliphatic epoxy resins, and glycidyl ether-type epoxy resins, and more preferably any one of naphthalene-type epoxy resins and aliphatic epoxy resins, from the viewpoint of significantly achieving the effects of the present invention. Among these, the epoxy resin (A) is preferably one containing a condensed cyclic skeleton such as a naphthalene-type epoxy resin, a naphthol-type epoxy resin, or anthracene-type epoxy resin. The epoxy resins may be used alone or in combination of two or more.

The resin composition preferably includes an epoxy resin having two or more epoxy groups per molecule as the epoxy resin (A). From the perspective of significantly achieving the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile components of the epoxy resin (A) is preferably 50% by mass or greater, more preferably 60% by mass or greater, and particularly preferably 70% by mass or greater.

Epoxy resins include those that are liquid at 20°C (hereinafter referred to as "liquid epoxy resins") and those that are solid at 20°C (hereinafter referred to as "solid epoxy resins"). The resin composition (A) may be a liquid epoxy resin, a solid epoxy resin, or a combination of liquid and solid epoxy resins. However, from the perspective of significantly achieving the effects of the present invention, it is preferred to use only liquid epoxy resins.

As the liquid epoxy resin, one having two or more epoxy groups in one molecule is preferred.

As the liquid epoxy resin, preferably, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin; epoxy resins such as epoxypropyl ester type epoxy resin, epoxypropyl amine type epoxy resin, phenol novolac type epoxy resin, epoxy resins having an ester skeleton, etc. are used. The epoxy resins are preferably epoxy resins of the type consisting of hexane, epoxy resins of the type consisting of glycidyl alcohol, epoxy resins of the type consisting of glycidylamine, epoxy resins of the type consisting of glycidyl ether, epoxy resins of the type consisting of glycidyl ether, and epoxy resins having a butadiene structure. Naphthalene epoxy resins, aliphatic epoxy resins, and epoxy resins of the type consisting of glycidyl ether are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-based epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epikote" manufactured by Mitsubishi Chemical Corporation. "828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (epoxypropylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemicals & Materials Co., Ltd.; "EX-721" (epoxypropyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide Examples include "2021P" (an epoxy resin with an ester backbone); "PB-3600" manufactured by DAICEL (an epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemicals & Materials (liquid 1,4-epoxypropylhexane-based epoxy resins); and "EX-992LEX" and "EX-992L" manufactured by Nagase ChemteX (epoxypropyl ester-based epoxy resins). These can be used individually or in combination.

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

Preferred solid epoxy resins include xylenol-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, naphthyl ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-based epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-based tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac-based epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-based epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", and "HP-720 "0H" (dicyclopentadiene-type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthyl ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H" manufactured by Nippon Kayaku Co., Ltd. , "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemicals & Materials Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemicals & Materials Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (xylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation Resins include: "YX8800" (anthracene-based epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-based epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-based epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-based epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "jER1031S" (tetraphenylethane-based epoxy resin) manufactured by Mitsubishi Chemical Corporation. These can be used alone or in combination.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin (A), the mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:10, and particularly preferably 1:0.1 to 1:1. Within this mass ratio, the desired effects of the present invention are significantly achieved. Furthermore, a cured product with sufficient breaking strength is generally obtained.

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

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500, in order to significantly achieve the desired effects of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

(A) The epoxy resin content is preferably 1% by mass or greater, more preferably 3% by mass or greater, and particularly preferably 4% by mass or greater, based on 100% by mass of the non-volatile components in the resin composition, from the perspective of obtaining a cured product exhibiting excellent mechanical strength and insulating reliability. The upper limit of the epoxy resin content is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less, from the perspective of significantly achieving the desired effects of the present invention. Furthermore, in the present invention, the content of each component in the resin composition is the value based on 100% by mass of the non-volatile components in the resin composition, unless otherwise specified.

From the perspective of obtaining a cured product exhibiting excellent mechanical strength and insulating reliability, the content of the (A) epoxy resin is preferably 10% by mass or greater, more preferably 20% by mass or greater, and particularly preferably 30% by mass or greater, based on 100% by mass of the resin component in the resin composition. From the perspective of significantly achieving the desired effects of the present invention, the upper limit of the epoxy resin content is preferably 75% by mass or less, more preferably 70% by mass or less, and particularly preferably 65% by mass or less. The term "resin component" refers to the components of the resin composition other than the (C) inorganic filler, which are non-volatile components.

<(B) At least one curing agent selected from an acid anhydride curing agent, an amine curing agent, and a phenol curing agent> The resin composition contains (B) at least one curing agent selected from an acid anhydride curing agent, an amine curing agent, and a phenol curing agent as component (B). Curing agents generally react with component (A) to cure the resin composition. However, in particular, by including such curing agents in the resin composition, in addition to the function of reacting with component (A) to cure the resin composition, a cured product with suppressed warping and flow marks can be obtained. Component (B) may be used alone or in combination of two or more.

Examples of the acid anhydride curing agent include those 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, homodimethylbenzene. Pyromellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonium tetracarboxylic 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), styrene-maleic acid resin copolymerized with maleic acid, and other polymeric anhydrides.

Examples of commercially available anhydride hardeners include "MH-700" manufactured by Shin Nippon Chemical Co., Ltd.

Examples of amine-based hardeners include those having one or more amino groups per molecule, such as aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among these, aromatic amines are preferred from the perspective of achieving the desired effects of the present invention. Amine-based hardeners are preferably primary or secondary amines, and more preferably primary amines. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfonate, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonate, 3,3'-diaminodiphenylsulfonate, metaphenylenediamine, metaxylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-aminobenzidine), -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)sulfonium, bis(4-(3-aminophenoxy)phenyl)sulfonium, etc.

Amine hardeners that can be used are commercially available products, such as "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard A-B", and "Kayahard A-S" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

Examples of phenolic hardeners include those containing one or more, preferably two or more, hydroxyl groups bonded to aromatic rings (such as benzene rings and naphthalene rings) per molecule. Compounds containing hydroxyl groups bonded to benzene rings are particularly preferred. Furthermore, from the perspective of heat resistance and water resistance, phenolic hardeners having a novolac structure are preferred. Furthermore, from the perspective of adhesion, nitrogen-containing phenolic hardeners are preferred, and phenolic hardeners containing a tris-indium skeleton are even more preferred. In particular, phenolic novolac hardeners containing a tris-indium skeleton are particularly preferred, as they offer excellent heat resistance, water resistance, and adhesion.

Specific examples of phenolic hardeners include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemicals; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku; and "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", and "LA-135" manufactured by DIC Corporation. 6", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165"; "GDP-6115L", "GDP-6115H", "ELPC75" manufactured by Qunrong Chemical Company; "2,2-Diallylbisphenol A" manufactured by Sigma-Aldrich Company, etc.

From the viewpoint of significantly achieving the effects of the present invention, the content of component (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, and is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

When the number of epoxy groups in component (A) is assumed to be 1, the number of active groups in component (B) is preferably 0.1 or greater, more preferably 0.3 or greater, and particularly preferably 0.5 or greater, and is preferably 2 or less, more preferably 1.8 or less, and particularly preferably 1.5 or less. Herein, the "number of epoxy groups in component (A)" refers to the total value obtained by dividing the mass of the nonvolatile components of component (A) present in the resin composition by the epoxy equivalent. Furthermore, the "number of active groups in component (B)" refers to the total value obtained by dividing the mass of the nonvolatile components of the hardener (B) present in the resin composition by the active group equivalent. Since the number of active groups of the curing agent (B) is within the aforementioned range, assuming the number of epoxy groups in the component (A) is 1, the desired effects of the present invention can be significantly achieved.

<(C) Polyester Polyol Resin with an Aliphatic Structure> The resin composition contains a polyester polyol resin (C) with an aliphatic structure as component (C). The aliphatic structure in component (C) imparts flexibility to the cured resin composition, resulting in suppressed warping. Furthermore, the functional groups of the polyester polyol in component (C) enhance compatibility with other components in the resin composition to a level that suppresses warping and flow marks. This results in a cured product with high bond strength and suppressed warping and flow marks. Furthermore, because component (C) imparts flexibility to the cured resin composition, it acts to mitigate stress in the cured product, thereby reducing the coefficient of linear thermal expansion (CTE) of the cured product. Component (C) can be used alone or in combination of two or more.

From the perspective of obtaining a cured product having high joint strength while also suppressing warping and flow marks, the content of component (C) is 1 mass% or greater, preferably 1.2 mass% or greater, more preferably 1.5 mass% or greater, and particularly preferably 2 mass% or greater, based on 100 mass% of the non-volatile components in the resin composition. From the perspective of obtaining a cured product having excellent joint strength and linear thermal expansion coefficient, the upper limit is 20 mass% or less, preferably 15 mass% or less, more preferably 10 mass% or less, and particularly preferably 8 mass% or less.

From the perspective of suppressing curl and flow marks in the cured product while simultaneously improving bond strength and, consequently, hydrolyzability, component (C) is preferably a resin having a polyester-derived structure and a polyol-derived structure. Such a resin can be obtained, for example, by reacting a polyol with a polycarboxylic acid. In component (C), the polyester-derived structure and the polyol-derived structure are aliphatic.

From the perspective of improving compatibility and bonding strength with the epoxy resin (A), the terminal of the molecular chain of component (C) is preferably a hydroxyl group or a carboxyl group, more preferably a hydroxyl group. The number of hydroxyl groups and carboxyl groups contained in component (C) is preferably 2 or more, more preferably 6 or less, particularly preferably 4 or less, even more preferably 3 or less, and particularly preferably 2 per molecule.

From the viewpoint of significantly achieving the effects of the present invention, the structure derived from the polyol is preferably 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-} ), _and more preferably a propylene oxide structure.

Examples of polyols include linear aliphatic polyols such as polyethylene glycol, polypropylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butanediol, and polytetramethylene ether glycol; and polyols with alicyclic structures such as cyclohexanedimethanol. Of these, linear aliphatic polyols are preferred. Polyols may be used alone or in combination of two or more.

The number average molecular weight of the polyol is preferably 50 or more, more preferably 1500 or less, even more preferably 1000 or less, and even more preferably 700 or less.

Commercially available polyols can be used. Examples of commercially available polyols include "Polypropylene glycol, diol type, 3,000" and "Polyethylene glycol 1540" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and "Polytetramethylene ether glycol PTMG1000" manufactured by Mitsubishi Chemical Corporation.

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; lactones such as ε-caprolactone; and anhydrides or esters thereof.

The polycarboxylic acid may be used alone or in combination of two or more. The polycarboxylic acid is preferably an aliphatic polycarboxylic acid or a lactone, more preferably a lactone. Commercially available polycarboxylic acids may be used. Examples of commercially available polycarboxylic acids include "Placcel M" manufactured by DAICEL.

To achieve a cured product with high bond strength while minimizing warping and flow marks, component (C) preferably has a functional group. Examples of such functional groups include hydroxyl groups, carboxyl groups, amino groups, acid anhydride groups, vinyl groups, allyl groups, and maleimide groups. Hydroxyl groups are particularly preferred.

Component (C) can be produced, for example, by reacting a polyol with a polycarboxylic acid. The reaction temperature is preferably 80°C or higher, more preferably 100°C or higher, and preferably 200°C or lower, more preferably 150°C or lower. The reaction time is preferably 1 hour or longer, more preferably 100 hours or shorter.

During the reaction, a catalyst may be used as needed. Examples of the catalyst include tin-based catalysts such as tin(II) 2-ethylhexanoate and dibutyltin oxide; titanium-based catalysts such as tetraisopropyl titanium and tetrabutyl titanium; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid. The catalyst may be used alone or in combination of two or more.

From the perspective of efficient reaction, the content of the catalyst is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, based on 100 parts by mass of the total of the polyol and the polycarboxylic acid.

From the perspective of significantly achieving the effects of the present invention, the hydroxyl value of component (C) is preferably 2 mgKOH/g or greater, more preferably 4 mgKOH/g or greater, particularly preferably 6 mgKOH/g or greater, 10 mgKOH/g or greater, 25 mgKOH/g or greater, 30 mgKOH/g or greater, or 35 mgKOH/g or greater, and is preferably 450 mgKOH/g or less, more preferably 100 mgKOH/g or less, and particularly preferably 50 mgKOH/g or less, 45 mgKOH/g or less, or 40 mgKOH/g or less. The hydroxyl value can be measured by a method in accordance with JIS K0070.

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

From the perspective of achieving a cured product that suppresses both warping and flow marks, the number average molecular weight of component (C) is preferably 500 or greater, more preferably 1000 or greater, even more preferably 2000 or greater, and even more preferably 3000 or greater, and is preferably 15000 or less, more preferably 12000 or less, and even more preferably 10000 or less. The number average molecular weight can be measured using GPC (gel permeation chromatography).

The solubility parameter (SP value) of component (C) is preferably 6.5 or higher, more preferably 7.0 or higher, and particularly preferably 7.5 or higher, from the viewpoint of improving compatibility, and is preferably 22 or lower, more preferably 21 or lower, and particularly preferably 20 or lower. The solubility parameter can be calculated using Fedors' theory.

From the viewpoint of improving the fluidity during compression molding, the melting point of component (C) is preferably -20°C or higher, more preferably -15°C or higher, and particularly preferably 0°C or higher, and is preferably 100°C or lower, more preferably 90°C or lower, and particularly preferably 80°C or lower.

When the content of component (A) when the non-volatile components in the resin composition are assumed to be 100% by mass is represented by a1, and the content of component (C) when the non-volatile components in the resin composition are assumed to be 100% by mass is represented by c1, a1/c1 is preferably 0.1 or greater, more preferably 0.3 or greater, and even more preferably 0.5 or greater, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting a1/c1 within this range, the effects of the present invention can be significantly achieved.

When the content of component (B) is b1, assuming the non-volatile components in the resin composition to be 100% by mass, b1/c1 is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting b1/c1 within this range, the effects of the present invention can be significantly achieved.

<(D) Inorganic Filler> The resin composition contains (D) an inorganic filler (component D). By incorporating (D) an inorganic filler into the resin composition, a cured product having a low coefficient of linear thermal expansion can be obtained.

Inorganic compounds are used as the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silica oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, hydroaluminite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanium oxide, calcium titanium oxide, magnesium titanium oxide, bismuth titanium oxide, titanium oxide, zirconium oxide, barium titanium oxide, barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is particularly preferred. (C) The inorganic filler may be used alone or in combination of two or more.

Examples of commercially available inorganic fillers (D) include "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C," "YA050C," "YA050C-MJE," and "YA010C" manufactured by ADMATECHS; "UFP-30" manufactured by DENKA Corporation; "Silfill NSS-3N," "Silfill NSS-4N," and "Silfill NSS-5N" manufactured by Tokuyama Corporation; and "SC2500SQ," "SO-C4," "SO-C2," "SO-C1," and "SC2050-SXF" manufactured by ADMATECHS.

(D) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 10 μm or less, more preferably 7 μm or less, and particularly preferably 5 μm or less, from the viewpoint of significantly achieving the desired effects of the present invention.

(D) The average particle size of an inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, a particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the median particle size can be used as the average particle size for measurement. The measurement sample can be 100 mg of an inorganic filler and 10 g of methyl ethyl ketone weighed in a vial and ultrasonically dispersed for 10 minutes. For the measurement sample, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source used is set to blue and red. The particle size distribution of the inorganic filler on a volume basis is measured using a flow cell method. From the obtained particle size distribution, the average particle size is calculated as the median particle size. Examples of laser diffraction particle size distribution measuring devices include the LA-960 manufactured by Horiba, Ltd. and the SALD-2200 manufactured by Shimadzu Corporation.

(D) The specific surface area of the inorganic filler is preferably 1 ^m² /g or greater, more preferably 2 ^m² /g or greater, and particularly preferably 3 ^m² /g or greater, from the perspective of significantly achieving the desired effects of the present invention. While there is no particular upper limit, it is preferably 60 ^m² /g or less, 50 ^m² /g or less, or 40 ^m² /g or less. The specific surface area of the inorganic filler is measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210, manufactured by MOUNTECH) by adsorbing nitrogen onto the sample surface and calculating the specific surface area using the BET multipoint method.

(D) Inorganic fillers are preferably treated with a surface treatment agent from the perspective of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane; aminosilane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; epoxysilane coupling agents such as 3-glycidoxypropyltrimethoxysilane; alkylsilane coupling agents such as 3-alkylpropyltrimethoxysilane; silane coupling agents; alkoxysilanes such as phenyltrimethoxysilane; organic silazane compounds such as hexamethyldisilazane; and titanium ester coupling agents. The surface treatment agent may be used alone or in combination of two or more.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-hydroxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM573" (N-phenyl- 3-Aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc.

From the perspective of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a specific range. Specifically, 0.2 to 5 parts by mass of the surface treatment agent is preferably applied to 100 parts by mass of the inorganic filler, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass.

The degree of surface treatment achieved by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. To improve the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ ^m² or greater, more preferably 0.1 mg/ ^m² or greater, and particularly preferably 0.2 mg/ ^m² or greater. On the other hand, to suppress increases in the melt viscosity of the resin varnish and the melt viscosity of the flaky form, the amount of carbon per unit surface area is preferably 1 mg/ ^m² or less, more preferably 0.8 mg/ ^m² or less, and particularly preferably 0.5 mg/ ^m² or less.

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

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 70% by mass or more, and particularly preferably 75% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, and is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

<(E) Hardening Accelerator> In addition to the above-mentioned components, the resin composition may further contain a hardening accelerator as component (E) as an optional component.

Examples of component (E) include epoxy resin curing accelerators such as phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators; and thermal polymerization curing accelerators such as peroxide-based curing accelerators. Component (E) may be used alone or in combination of two or more.

Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Preferred are triphenylphosphine and tetrabutylphosphonium decanoate.

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

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tris-imidazolium, 2,4-diamino- 6-[2'-Undecylimidazolyl-(1')]-ethyl-s-triacontium, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triacontium, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triacontium isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy Imidazole compounds such as methylimidazole, 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 adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercially available product can be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based hardening accelerator include cyanoguanidine, 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, 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, 1-(o-tolyl)biguanidine, etc., preferably cyanoguanidine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of metal hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonikel complexes such as nickel(II) acetylacetonate, and organomethane complexes such as manganese(II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, and zinc stearate.

Examples of peroxide-based curing accelerators include di-tert-butyl peroxide, tert-butyl isopropyl peroxide, tert-butyl peroxyacetate, α,α'-di(tert-butylperoxy)diisopropylbenzene, tert-butyl peroxylaurate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, and tert-butyl peroxybenzoate.

Examples of commercially available peroxide-based curing accelerators include "Perhexyl D," "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Percumyl P," and "Percumyl D," all manufactured by NOF Corporation.

From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (E) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, and is preferably 1% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.5% by mass or less.

From the viewpoint of significantly achieving the desired effects of the present invention, the content of component (E) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 3% by mass or less, based on the resin component in the resin composition being 100% by mass.

<(F) Other Additives> In addition to the components listed above, the resin composition may further contain other additives as optional components. Examples of such additives include colorants, pigments, thermoplastic resins, thickeners, defoamers, leveling agents, and adhesion enhancers. These additives may be used singly or in combination. The content of each additive can be determined as appropriate by the industry.

The resin composition may further contain an arbitrary solvent as a volatile component. As the solvent, for example, an organic solvent can be cited. Moreover, the solvent may be used alone or in combination of two or more types in an arbitrary ratio. The smaller the amount of solvent, the better. Relative to 100% by mass of the non-volatile components in the resin composition, the amount of solvent is preferably 3% by mass or less, more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and particularly preferably contains no solvent (0% by mass). Moreover, when the amount of solvent in the resin composition is so small, it 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.

The method for preparing the resin composition of the present invention is not particularly limited. For example, a method of adding the ingredients to a solvent as needed and mixing and dispersing them using a rotary mixer or the like can be cited.

<Physical Properties and Applications of Resin Compositions> A cured product using the above-described resin composition exhibits flow mark suppression. Therefore, the cured product provides an insulating layer or sealing layer with suppressed flow mark generation. Specifically, the resin composition is compression-molded onto a silicon wafer to form a resin composition layer, which is then heated to obtain a cured product layer. This process suppresses flow mark generation on the surface of the cured product. Flow mark generation can be measured in detail using the method described in the Examples below.

The cured product obtained by heat curing the resin composition at 180°C for 90 minutes shows excellent bonding strength. Bonding strength can be expressed, for example, as shear strength. Therefore, the cured product generally provides an insulating layer or sealing layer with excellent shear strength. The shear strength can indicate the difficulty of peeling off when a force is applied in the in-plane direction perpendicular to the thickness direction. Specifically, consider the case where a cured material layer is formed on a surface formed of a certain material (such as polyimide) by a cured material of a resin composition. In this case, the magnitude of the force applied in the in-plane direction to the cured material layer at which the cured material layer will peel off from the aforementioned surface is expressed as shear strength. The shear strength is preferably 1.7 kgf/mm² ^or greater, more preferably 2.0 kgf/ ^mm² or greater, and even more preferably 2.5 kgf/mm² or ^greater . There is no particular upper limit, but it can be set to 10 kgf/ ^mm² or less. Shear strength can be measured according to the method described in the Examples below.

The cured product after thermally curing the resin composition at 180°C for 90 minutes exhibits the characteristic of suppressed warp. Therefore, the cured product provides an insulating layer or sealing layer with suppressed warp. Specifically, the resin composition is compression-molded onto a silicon wafer to form a resin composition layer. The resin composition layer is thermally cured to obtain a sample substrate. Using a shadow moire measurement device, the warp of the sample substrate at 25°C is determined in accordance with JEITA EDX-7311-24, the standard of the Electronics and Information Technology Industries Association. The warp is preferably less than 2 mm. The details of the measurement of the warp amount can be measured according to the method described in the embodiments described below.

The cured resin composition, after heat curing at 150°C for 60 minutes, exhibits a low coefficient of linear thermal expansion (CTE). Therefore, the cured product provides an insulating layer or sealing layer with a low coefficient of linear thermal expansion. The coefficient of linear thermal expansion (CTE) is preferably less than 15 ppm/°C, more preferably less than 13 ppm/°C, and even more preferably less than 13 ppm/°C. The lower limit is not particularly limited, but can be set to 0.01 ppm/°C or higher. The coefficient of linear thermal expansion can be measured according to the method described in the Examples below.

Due to the aforementioned properties, the resin composition is suitable for use as a resin composition for sealing electronic devices such as organic EL devices and semiconductors (sealing resin composition). It is particularly suitable for use as a resin composition for sealing semiconductors (semiconductor sealing resin composition), and more preferably as a resin composition for sealing semiconductor chips (semiconductor chip sealing resin composition). Furthermore, the resin composition can be used not only for sealing but also as an insulating layer for insulating purposes. For example, the resin composition can be suitably used as a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for insulating layer of semiconductor chip package) and a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) (resin composition for insulating layer of a circuit board).

Examples of semiconductor chip packages include FC-CSP, MIS-BGA, ETS-BGA, fan-out WLP (wafer level package), fan-in WLP, fan-out PLP (panel level package), and fan-in PLP.

Furthermore, the resin composition can be used as an underfill material, for example, as a MUF (molding under filling) material used after a semiconductor chip is connected to a substrate.

Furthermore, the resin composition can be used in a wide range of applications such as resin sheets, prepregs, and other thin-sheet laminate materials, solder resists, die-bonding materials, buried hole resins, and component embedding resins.

[Resin Sheet] The resin sheet of the present invention comprises a support and a resin composition layer disposed on the support. The resin composition layer is a layer containing the resin composition of the present invention and is typically formed of a resin composition.

From the perspective of reducing thickness, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, and even more preferably 500 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, or 200 μm or less. There is no particular lower limit to the thickness of the resin composition layer; for example, it can be 1 μm or more, 5 μm or more, or 10 μm or more.

Examples of the support include films made of plastic materials, metal foils, and release paper, preferably films made of plastic materials or metal foils.

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

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

The surface of the support body that is bonded to the resin composition layer may be subjected to matte treatment, corona treatment, anti-static treatment, etc.

Alternatively, a support with a release layer may be used, wherein the surface that contacts the resin composition layer includes a release layer. Examples of release agents used for the release layer of the support with a release layer include at least one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available release agents include release resin-based release agents such as "SK-1," "AL-5," and "AL-7" manufactured by LINTEC. In addition, as a support body with a release layer, for example, "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by UNITIKA can be cited.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, the thickness of the entire support with the release layer is preferably within the above range.

Resin sheets can be produced by applying a resin composition onto a support using a coating device such as a die coater. Alternatively, resin sheets can be produced by dissolving the resin composition in an organic solvent to prepare a resin varnish, which is then applied to the sheet. Adjusting the viscosity with a solvent improves coating properties. When using a resin varnish, it is typically dried after application to form a layer of the resin composition.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosol acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosol and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more in any ratio.

Drying can be carried out by known methods such as heating and hot air spraying. Drying conditions are such that the organic solvent content in the resin composition layer is generally 10% by mass or less, preferably 5% by mass or less. While this varies 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 organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

The resin sheet may include any layer other than the support and the resin component layer as needed. For example, in the resin sheet, a protective film that conforms to the support may be provided on the surface of the resin component layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust and the like from adhering to or damaging the surface of the resin component layer. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, the resin sheet can be rolled into a roll for storage.

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

Furthermore, the resin sheet can be used to seal 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.

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

Furthermore, resin sheets can be used in a wide range of other applications requiring high insulation reliability. For example, resin sheets can be used to form the insulation layer of circuit boards such as printed wiring boards.

[Circuit board] The circuit board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. This circuit board can be manufactured, for example, by a manufacturing method comprising the following steps (1) and (2). (1) A step of forming a resin composition layer on a substrate. (2) A step of thermally curing the resin composition layer to form an insulating layer.

In step (1), a substrate is prepared. As the substrate, for example, a glass epoxy substrate, a metal substrate (stainless steel or cold-rolled steel plate (SPCC)), a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, etc. can be cited. In addition, the substrate may also have a metal layer such as copper foil on the surface as a part of the substrate. For example, a substrate having a first metal layer and a second metal layer that can be peeled off on both surfaces can be used. When such a substrate is used, a conductive layer having a wiring layer that can function as a circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. Examples of materials for the metal layer include copper foil, copper foil with a carrier, and the material for the conductor layer described below. Copper foil is preferred. Commercially available substrates with such a metal layer can be used, for example, "Micro Thin," an ultra-thin copper foil with a carrier manufactured by Mitsui & Co., Ltd.

Furthermore, a conductive layer may be formed on one or both surfaces of the substrate. In the following description, a component comprising a substrate and a conductive layer formed on the surface of the substrate is also appropriately referred to as a "substrate with a wiring layer." Examples of conductive materials contained in the conductive layer include materials comprising one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As conductive materials, a single metal or an alloy may be used. Examples of alloys include alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the perspectives of versatility in forming the conductive layer, cost, and ease of patterning, preferred are chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys as alloys. More preferred are chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and nickel-chromium alloys, with copper as single metal being particularly preferred.

The conductive layer may be patterned, for example, to function as a wiring layer. While the line (circuit width)/space (width between circuits) ratio of the conductive layer is not particularly limited, it is preferably 20/20 μm or less (i.e., a spacing of 40 μm or less), more preferably 10/10 μm or less, particularly preferably 5/5 μm or less, even more preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The spacing does not necessarily need to be uniform throughout the conductive layer. For example, the minimum spacing of the conductive layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

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

The conductive layer can be formed, for example, by a method comprising the following steps: laminating a dry film (photosensitive resist film) on a substrate; exposing and developing the dry film under specific conditions using a photomask to form a pattern to obtain a patterned dry film; forming a conductive layer by a plating method such as electrolytic plating using the developed patterned dry film as a plating mask; and peeling off the patterned dry film. A photosensitive dry film made of 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 lamination conditions between the substrate and the dry film can be the same as the lamination conditions between the substrate and the resin sheet described below. The dry film can be peeled off using an alkaline peeling liquid such as sodium hydroxide solution.

After preparing the substrate, a resin composition layer is formed on the substrate. When a conductive layer is formed on the surface of the substrate, the resin composition layer is preferably formed in such a manner that the conductive layer is embedded in the resin composition layer.

The resin composition layer is formed, for example, by laminating a resin sheet and a substrate. This lamination can be performed, for example, by heat-pressing the resin sheet against the substrate from the side of the support, thereby adhering the resin composition layer to the substrate. Examples of the member for heat-pressing the resin sheet against the substrate (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller). Furthermore, it is preferable not to press the heat-pressing member directly against the resin sheet, but rather to press the resin sheet through an elastic material such as heat-resistant rubber, so that the resin sheet fully follows the surface irregularities of the substrate.

Lamination of the substrate and the resin sheet can be performed using a vacuum lamination method. The heat-pressing temperature during vacuum lamination is preferably between 60°C and 160°C, more preferably between 80°C and 140°C. The heat-pressing pressure is preferably between 0.098 MPa and 1.77 MPa, more preferably between 0.29 MPa and 1.47 MPa. The heat-pressing time is preferably between 20 seconds and 400 seconds, more preferably between 30 seconds and 300 seconds. Lamination is preferably performed under reduced pressure at a pressure of 13 hPa or less.

After lamination, the laminated resin sheets can be smoothed by applying pressure under normal pressure (atmospheric pressure), for example, from the side of the support. The pressure conditions for the smoothing treatment can be the same as those for the lamination heat and pressure treatment described above. Furthermore, lamination and smoothing can also be performed continuously using a vacuum laminator.

The resin composition layer can be formed, for example, by compression molding. Specifically, compression molding involves preparing an upper mold and a lower mold. The resin composition is applied to a substrate. The substrate coated with the resin composition is then mounted on the lower mold. The upper and lower molds are then closed, and heat and pressure are applied to the resin composition to perform compression molding.

The specific operation of the compression molding method can be as follows. An upper mold and a lower mold are prepared as compression molding dies. A resin composition is placed in the lower mold. A substrate is attached to the upper mold. The upper and lower molds are then closed so that the resin composition placed in the lower mold contacts the substrate attached to the upper mold. Heat and pressure are applied to perform compression molding.

The molding conditions for compression molding vary depending on the composition of the resin composition. The mold temperature during molding is preferably a temperature that allows the resin composition to exhibit excellent compression moldability, for example, preferably 80°C or higher, more preferably 100°C or higher, and particularly preferably 120°C or higher, and preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. Furthermore, the pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, and particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or longer, more preferably 2 minutes or longer, and particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Typically, the mold is removed after the resin composition layer is formed. The mold can be removed before or after the resin composition layer is thermally cured.

After forming a resin composition layer on the substrate, the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but the curing temperature is generally in the range of 120°C to 240°C (preferably 150°C to 220°C, and 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, and more preferably 15 minutes to 90 minutes).

Before heat-hardening the resin composition layer, the resin composition layer may be subjected to a preliminary heat treatment at a temperature lower than the curing temperature. For example, before heat-hardening the resin composition layer, the resin composition layer may be preheated at a temperature generally above 50°C and below 120°C (preferably above 60°C and below 110°C, more preferably above 70°C and below 100°C) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, a circuit board having an insulating layer can be manufactured. Furthermore, the method for manufacturing a circuit board may further include an optional step. For example, when a resin sheet is used to manufacture the circuit board, the method may include the step of peeling off a support member from the resin sheet. The support member may be peeled off before or after the resin composition layer is thermally cured.

The manufacturing method of the circuit substrate 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, and for example, a flat grinding disc may be used to grind the surface of the insulating layer.

The manufacturing method of the circuit substrate may include, for example, the step (3) of connecting the conductive layer between layers, i.e., the step of opening a hole in the insulating layer. This allows holes such as through holes and through holes to 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 according to the design of the circuit substrate. Furthermore, step (3) can also be performed by grinding or polishing the insulating layer to achieve interlayer connection.

After forming the through-hole, it is preferable to perform a step to remove the adhesive residue within the through-hole. This step is also called a desmearing step. For example, when forming a conductive layer on an insulating layer via a plating step, a wet desmearing treatment can be performed on the through-hole. Alternatively, when forming a conductive layer on an insulating layer via a sputtering step, a dry desmearing step, such as a plasma treatment step, can be performed. Furthermore, the desmearing step can also be used to roughen the insulating layer.

Furthermore, before forming the conductive layer on the insulating layer, the insulating layer may be subjected to a roughening treatment. This roughening treatment typically roughens the surface of the insulating layer, including the surface within the through-hole. The roughening treatment can be either dry or wet. Examples of dry roughening treatments include plasma treatment. Examples of wet roughening treatments include sequentially performing a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution.

After forming the through-hole, a conductive layer is formed on the insulating layer. By forming the conductive layer at the location where the through-hole is formed, the newly formed conductive layer is connected to the conductive layer on the surface of the substrate, thereby achieving inter-layer connection. Examples of methods for forming the conductive layer include plating, sputtering, and evaporation, among which plating is preferred. In a suitable embodiment, a conductive layer having a desired wiring pattern is formed by plating on the surface of the insulating layer using a suitable method such as a semi-additive method or a full-additive method. Furthermore, when the support in the resin sheet is a metal foil, a conductive layer having a desired wiring pattern can be formed by a subtractive method. The material of the conductive layer formed can be a single metal or an alloy. Furthermore, the conductive layer may have a single-layer structure or a multi-layer structure including two or more layers of different types of materials.

Here, an example of an implementation form of forming a conductive layer on an insulating layer is described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After an electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or other processes to form a conductive layer having the desired wiring pattern. Furthermore, when forming the conductive layer, the dry film used in forming the mask pattern is the same as the dry film described above.

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

[Semiconductor Chip Package] A semiconductor chip package according to a first embodiment of the present invention includes the aforementioned circuit substrate and a semiconductor chip mounted on the circuit substrate. This semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit substrate.

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

An example of a bonding method is press-bonding a semiconductor chip to a circuit board. Press-bonding conditions typically include a temperature in the range of 120°C to 240°C (preferably 130°C to 200°C, and more preferably 140°C to 180°C), and a time in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

Another example of a bonding method is to reflow a semiconductor chip onto a circuit board. The reflow temperature can be set within a range of 120°C to 300°C.

After bonding the semiconductor chip to the circuit board, a molded underfill material can be used to fill the semiconductor chip. As the molded underfill material, the resin composition described above can be used, and a resin composition layer of the resin sheet described above can also be used.

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

The method for manufacturing a semiconductor chip package of such a fan-out WLP includes: (A) laminating a temporary fixing film onto a substrate, (B) temporarily fixing a semiconductor chip on the temporary fixing film, (C) laminating a resin composition of a resin sheet of the present invention onto the semiconductor chip, or applying the resin composition of the present invention onto the semiconductor chip and thermally curing the resin composition to form a sealing layer, (D) peeling off the substrate and the temporary fixing film from the semiconductor chip, (E) forming a redistribution layer (insulating layer) on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled, (F) forming a conductive layer (redistribution layer) on the redistribution formation layer (insulation layer), and (G) forming a solder resist layer on the conductive layer. Furthermore, the method for manufacturing a semiconductor chip package may include: (H) singulating a plurality of semiconductor chip packages into individual semiconductor chip packages.

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.

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

<Semiconductor Devices> A semiconductor device includes a semiconductor chip package. Examples of semiconductor devices include various semiconductor devices used in power products (such as computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and aircraft). [Examples]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Furthermore, in the following description, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "% by mass" respectively.

<Synthesis Example 1: Synthesis of Aliphatic Polyester Polyol Resin A> A reaction vessel was charged with 22.6 g of ε-caprolactone monomer ("Placcel M" manufactured by DAICEL), 10 g of polypropylene glycol, diol type, 3,000 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 1.62 g of tin(II) 2-ethylhexanoate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). The mixture was heated to 130°C under a nitrogen atmosphere and stirred for approximately 16 hours to allow the reaction to proceed. The resulting product was dissolved in chloroform, reprecipitated with methanol, and dried to obtain hydroxyl-terminated polyester polyol resin A with an aliphatic backbone. GPC analysis revealed an Mn of 9000.

<Synthesis Example 2: Synthesis of Aliphatic Polyester Polyol Resin B> 22.6 g of ε-caprolactone monomer ("Placcel M" manufactured by DAICEL), 10 g of polyethylene glycol 1540 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 1.3 g of tin(II) 2-ethylhexanoate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added to a reaction vessel. The mixture was heated to 130°C under a nitrogen atmosphere and stirred for approximately 16 hours to allow the reaction to proceed. The resulting product was dissolved in chloroform, reprecipitated with methanol, and dried to obtain hydroxyl-terminated polyester polyol resin B with an aliphatic backbone. GPC analysis revealed an Mn of 4500.

<Synthesis Example 3: Synthesis of Aliphatic Polyester Polyol Resin C> 22.6 g of ε-caprolactone monomer ("Placcel M" manufactured by DAICEL), 10 g of polytetramethylene ether glycol PTMG1000 (manufactured by Mitsubishi Chemical Corporation), and 1.3 g of tin(II) 2-ethylhexanoate (manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.) were added to a reaction vessel. The mixture was heated to 130°C under a nitrogen atmosphere and stirred for approximately 16 hours to allow the reaction to proceed. The resulting product was dissolved in chloroform, reprecipitated with methanol, and dried to obtain hydroxyl-terminated polyester polyol resin C with an aliphatic backbone. GPC analysis revealed an Mn of 3100.

<Inorganic Fillers Used> Silica A: Average particle size 9 μm, specific surface area 5.0 m ² /g, surface-treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.). Silica B: Average particle size 1.6 μm, specific surface area 3.4 m ² /g, surface-treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.). Alumina A: Average particle size 8.4 μm, specific surface area 0.9 m ² /g, surface-treated with KBM573 (manufactured by Shin-Etsu Chemical Co., Ltd.).

<Example 1> A mixer was used to uniformly disperse 8 parts of a naphthalene-based epoxy resin ("HP4032D" manufactured by DIC Corporation, epoxy equivalent weight 144 g/eq.), 6.6 parts of an aliphatic epoxy resin ("Celloxide 2021P" manufactured by DAICEL Corporation, epoxy equivalent weight 136 g/eq.), 2.5 parts of the polyester polyol A obtained in Synthesis Example 1, 0.5 parts of an amine-based curing agent ("Kayahard A-A" manufactured by Nippon Kayaku Co., Ltd.), 80 parts of silica A, and 0.4 parts of a curing accelerator ("2MA-OK-PW" manufactured by Shikoku Chemicals Co., Ltd.) to obtain Resin Composition 1.

<Example 2> Using a mixer, 3 parts of a naphthalene-based epoxy resin ("HP4032D" manufactured by DIC Corporation, epoxy equivalent weight 144 g/eq.), 3 parts of an aliphatic epoxy resin ("Celloxide 2021P" manufactured by DAICEL Corporation, epoxy equivalent weight 136 g/eq.), 4 parts of the polyester polyol A obtained in Synthesis Example 1, 10 parts of an acid anhydride-based hardener ("MH-700" manufactured by Shin Nippon Rika Chemical), 90 parts of silica B, and 0.5 parts of a hardening accelerator ("2MA-OK-PW" manufactured by Shikoku Chemical Co., Ltd.) were uniformly dispersed to obtain Resin Composition 2.

<Example 3> A mixer was used to uniformly disperse 8 parts of a naphthalene-based epoxy resin (DIC Corporation's "HP4032D," epoxy equivalent weight 144 g/eq.), 7 parts of an aliphatic epoxy resin (DAICEL Corporation's "Celloxide 2021P," epoxy equivalent weight 136 g/eq.), 1 part of 2,2'-diallylbisphenol A (DABPA, Yamato Chemical Industries, Ltd.), 2 parts of the polyester polyol A obtained in Synthesis Example 1, 80 parts of silica A, and 0.4 parts of a curing accelerator (Shikoku Chemicals Co., Ltd.'s "2MA-OK-PW") to obtain Resin Composition 3.

<Example 4> In Example 2, 90 parts of silica B was replaced with 120 parts of aluminum oxide A. Resin composition 4 was obtained in the same manner as in Example 2 except for the above.

Example 5: Using a mixer, 3 parts of a naphthalene-based epoxy resin ("HP4032D" manufactured by DIC Corporation, epoxy equivalent weight 144 g/eq.), 2 parts of an aliphatic epoxy resin ("Celloxide 2021P" manufactured by DAICEL Corporation, epoxy equivalent weight 136 g/eq.), 1 part of an epoxy propyl ether-based epoxy resin (polyether diol diglycidyl ether, "EX-992L" manufactured by Nagase ChemteX Corporation, epoxy equivalent weight 680 g/eq.), 9 parts of the polyester polyol A obtained in Synthesis Example 1, 10 parts of an acid anhydride-based hardener ("MH-700" manufactured by Shin Nippon Rika Chemical Co., Ltd.), and 10 parts of silica A were uniformly dispersed. 100 parts of propylene glycol and 0.5 parts of a curing accelerator ("2MA-OK-PW" manufactured by Shikoku Chemical Co., Ltd.) were added to obtain resin composition 5.

<Example 6> In Example 2, 4 parts of polyester polyol resin A were replaced with 4 parts of polyester polyol resin B. Resin composition 6 was obtained in the same manner as in Example 2 except for the above.

Example 7 In Example 3, 2 parts of polyester polyol resin A were replaced with 2 parts of polyester polyol resin C. Resin composition 7 was obtained in the same manner as in Example 3 except for the above.

<Example 8> In Example 5, one part of the epoxy resin (polyether glycol diglycyl ether, "EX-992L" manufactured by Nagase ChemteX, epoxy equivalent weight 680 g/eq.) was replaced with one part of the fluorene-based epoxy resin ("EG-280" manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent weight 460 g/eq.). Resin Composition 8 was obtained in the same manner as in Example 5 except for the above.

Comparative Example 1 In Example 1, 2.5 parts of polyester polyol A obtained in Synthesis Example 1 were omitted. Resin composition 9 was obtained in the same manner as in Example 1 except for the above.

Comparative Example 2 In Example 2, the amount of polyester polyol A obtained in Synthesis Example 1 was changed from 4 parts to 0.5 parts, and 90 parts of silica B was replaced with 100 parts of silica A. Resin composition 10 was obtained in the same manner as in Example 2 except for the above.

Comparative Example 3 In Example 2, the amount of polyester polyol A obtained in Synthesis Example 1 was changed from 4 parts to 35 parts, and 90 parts of silica B was replaced with 100 parts of silica A. Resin composition 11 was obtained in the same manner as in Example 2 except for the above.

<Flow Mark Evaluation> The resin compositions produced in the Examples and Comparative Examples were compression-molded onto a 12-inch silicon wafer using a compression molding machine (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes) to form a 300μm thick resin layer. The layers were then heated at 150°C for 60 minutes. The surface of the resin layer was visually inspected for flow marks and evaluated using the following criteria. ○: No flow marks. ×: Flow marks present.

<Evaluation of Shear Strength> A 5mm-high cylindrical shape of the resin composition prepared in the Examples and Comparative Examples was filled onto a polyimide-coated silicon wafer using a 4mm-diameter hollowed-out silicone rubber frame. After heating at 180°C for 90 minutes, the silicone rubber frame was removed to produce a test piece consisting of the cured resin composition. The shear strength of the interface between the polyimide and the cured resin composition was measured using a bond tester (4000 series, manufactured by Dage) at a head position of 1mm from the silicon wafer and a head speed of 700μm/s. Five tests were performed, and the average value was used for evaluation using the following criteria. ◎: Shear strength of 2.5kgf/ ^mm² or greater. ○: Shear strength is 2.0 kgf/mm ² or more and less than 2.5 kgf/mm ^2. △: Shear strength is 1.7 kgf/mm ² or more and less than 2.0 kgf/mm ^2. ×: Shear strength is less than 1.7 kgf/mm ² .

<Warp Measurement> The resin compositions prepared in the Examples and Comparative Examples were compression-molded onto a 12-inch silicon wafer using a compression molding machine (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes) to form a 300μm thick resin composition layer. The resin composition layer was then thermally cured at 180°C for 90 minutes. This yielded a sample substrate containing the silicon wafer and the cured resin composition layer. The warp of these sample substrates was measured at 25°C using a shadow overlay measurement system (Akorometrix "Thermoire AXP"). Measurements were conducted in accordance with JEITA EDX-7311-24, a standard of the Electronics and Information Technology Industries Association. Specifically, a hypothetical plane, calculated using the least squares method for all data points on the substrate surface within the measurement area, was used as a reference plane. The difference between the minimum and maximum values perpendicular to this reference plane was calculated as the warp value, and evaluation was performed using the following criteria. ◎: Warp less than 1.8mm. ○: Warp 1.8mm or more and less than 2mm. ×: Warp 2mm or more.

<Measurement of Coefficient of Linear Thermal Expansion (CTE)> The resin compositions prepared in Examples and Comparative Examples were compression-molded onto a 12-inch silicon wafer that had been demolded using a compression molding machine (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes) to form a 300μm thick resin layer. The resin layer was then peeled from the demolded 12-inch silicon wafer and thermally cured by heating at 150°C for 60 minutes to produce cured samples. The cured samples were then cut into 5mm wide and 15mm long sections to obtain test pieces. The test piece was subjected to thermomechanical analysis using the tensile loading method using a thermomechanical analyzer (RIGAKU "ThermoPlus TMA8310"). Specifically, the test piece was mounted in the analyzer and subjected to two consecutive measurements under the conditions of a 1g load and a heating rate of 5°C/minute. The coefficient of linear thermal expansion (ppm/°C) in the planar direction over the range of 25°C to 150°C was calculated during the second measurement and evaluated using the following criteria: ◎: Less than 13 ppm/°C ○: 13 ppm or higher and less than 15 ppm/°C ×: 15 ppm/°C or higher.

* In the table, the contents of component (C) and component (D) are based on the non-volatile components in the resin composition being taken as 100% by mass.

In Examples 1 to 8, even when the component (E) was not contained, it was confirmed that the same results as those of the above-mentioned Examples were achieved, although the degree of improvement was different.

Claims (16)

A resin composition comprising: (A) an epoxy resin, (B) at least one curing agent selected from an anhydride curing agent, an amine curing agent, and a phenol curing agent, (C) a polyester polyol resin having an aliphatic structure formed from a lactone and a polyol, and (D) an inorganic filler; wherein component (C) has a number average molecular weight of 2000 or greater, and the content of component (C) is 1% by mass or greater and 20% by mass or less, based on 100% by mass of the non-volatile components in the resin composition. A resin composition comprising: (A) an epoxy resin, (B) at least one curing agent selected from an anhydride curing agent, an amine curing agent, and a phenol curing agent, (C) a polyester polyol resin having an aliphatic structure, and (D) an inorganic filler; wherein, based on 100% by mass of the non-volatile components in the resin composition, the content of component (C) is 1% by mass to 20% by mass, and based on 100% by mass of the non-volatile components in the resin composition, the content of component (D) is 60% by mass or more. A resin composition comprising: (A) an epoxy resin, (B) at least one hardener selected from an amine-based hardener having a primary amine and a phenol-based hardener, (C) a polyester polyol resin having an aliphatic structure, and (D) an inorganic filler; wherein the content of component (C) is 1% by mass or more and 20% by mass or less, based on 100% by mass of the non-volatile components in the resin composition. The resin composition of any one of claims 1 to 3, wherein component (A) comprises a condensed ring skeleton. The resin composition according to any one of claims 1 to 3, wherein the terminal of component (C) is either a hydroxyl group or a carboxyl group. The resin composition according to any one of claims 1 to 3, wherein component (C) is a resin having a structure derived from a polyol. The resin composition according to any one of claims 1 to 3, wherein component (C) is a resin having a structure derived from polyester and a structure derived from polyol. The resin composition of claim 6, wherein the structure derived from the polyol has an alkylene oxide structure having 2 or more carbon atoms. The resin composition of claim 7, wherein the structure derived from the polyol comprises any one of an ethylene oxide structure, a propylene oxide structure, and a butylene oxide structure. The resin composition of claim 1 or 3, wherein the content of component (D) is 60% by mass or greater, taking the non-volatile components in the resin composition as 100% by mass. The resin composition according to any one of claims 1 to 3, which is used as a sealing layer. A resin sheet comprising a support and a resin composition layer disposed on the support and comprising the resin composition of any one of claims 1 to 11. A circuit board comprising a cured material layer formed by curing the resin composition according to any one of claims 1 to 11. A semiconductor chip package comprises a circuit substrate as claimed in claim 13 and a semiconductor chip mounted on the circuit substrate. A semiconductor chip package comprising a semiconductor chip sealed by the resin composition of any one of claims 1 to 11 or the resin sheet of claim 12. A semiconductor device comprising the semiconductor chip package of claim 14 or 15.