TWI888561B - Resin composition - Google Patents

Abstract

The present invention provides a resin composition that can obtain a cured product having high bonding strength and suppressed warping; a resin sheet, a circuit board, and a semiconductor chip package using the resin composition. The resin composition of the present invention is a resin composition comprising (A) an epoxy resin, (B) at least one curing agent selected from anhydride curing agents, amine curing agents, and phenolic curing agents, (C) a polyester polyol resin having an aromatic structure, and (D) an inorganic filler, wherein the content of the component (C) is 2% by mass or more and 20% by mass or less when the non-volatile components in the resin composition are set to 100% by mass.

Description

Resin composition

The present invention relates to a resin composition, and further to a resin sheet, a circuit substrate and a semiconductor chip package containing the resin composition.

In recent years, the demand for small, high-function electronic devices such as smartphones and tablet devices has increased, and with this, there is a demand for highly functional insulating materials that can be used as sealing layers and insulating layers of such small electronic devices. As such insulating materials, those described in patent documents 1 and 2 are known. [Prior technical documents] [Patent document]

[Patent Document 1] International Publication No. 2019/044803 [Patent Document 2] International Publication No. 2019/131413

[Problems to be solved by the invention]

In recent years, there has been a demand for smaller electronic devices, and the insulating layer or sealing layer used in the electronic devices has been required to be thinner. The insulating layer or sealing layer has a tendency to warp easily if it is thin, and an insulating layer or sealing layer that can suppress the warp is desired. In addition, the insulating layer or sealing layer is also expected to have a high bonding strength with other layers.

The present invention was created in view of the above-mentioned problem, and its purpose is to provide a resin composition that can obtain a cured product with high bonding strength and suppressed warping; a resin sheet, a circuit substrate and a semiconductor chip package using the resin composition. [Means for solving the problem]

As a result of the active research to solve the above-mentioned problems, the inventors of the present invention have found that the above-mentioned problems can be solved by combining a resin composition comprising (A) an epoxy resin, (B) at least one curing agent selected from anhydride curing agents, amine curing agents and phenolic curing agents, (C) a polyester polyol resin having a specific amount of aromatic structure, and (D) an inorganic filler, thereby 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 aromatic structure, and (D) an inorganic filler, wherein the content of component (C) is 2% by mass to 20% by mass when the non-volatile components in the resin composition are taken as 100% by mass. [2] A resin composition as described in [1], wherein component (A) comprises a condensed ring skeleton. [3] A 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 of any one of [1] to [3], wherein the content of component (D) is 60% by mass or more and 95% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. [5] The resin composition of any one of [1] to [4], wherein component (C) is a resin having a structure derived from polyester and a structure derived from polyol. [6] The resin composition of [5], wherein the structure derived from polyol includes any one of an ethylene oxide structure, a propylene oxide structure and a butylene oxide structure. [7] The resin composition of any one of [1] to [6], wherein component (C) has a bisphenol skeleton. [8] A resin composition as described in any one of [1] to [7], wherein when the content of component (C) in the resin composition is 100% by mass and the content of component (D) in the resin composition is 100% by mass, d1/c1 is 5 to 70. [9] A resin composition as described in any one of [1] to [8], which is used as a sealing layer. [10] A resin sheet comprising a support and a resin composition layer provided on the support and comprising the resin composition as described in any one of [1] to [9]. [11] A circuit substrate comprising a hardened material layer formed by a hardened material of a resin composition as described in any one of [1] to [9]. [12] A semiconductor chip package comprising a circuit substrate as described in [11] and a semiconductor chip mounted on the circuit substrate. [13] A semiconductor chip package comprising a semiconductor chip sealed by a resin composition as described in any one of [1] to [9] or a resin sheet as described in [10]. [Effect of the invention]

According to the present invention, a resin composition capable of obtaining a cured product having high bonding strength and suppressed warping can be provided; and a resin sheet, a circuit substrate and a semiconductor chip package using the resin composition can be provided.

The following embodiments and examples are provided to explain the present invention in detail. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented within the scope of the patent application of the present invention and its equivalent scope.

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

The cured product of the resin composition can make use of its excellent properties and can be preferably used as an insulating layer or a sealing layer of a circuit substrate and a semiconductor chip package, and is particularly preferably used as a sealing layer.

The resin composition may further include an arbitrary component in combination with the components (A) to (D). Examples of the arbitrary component include (E) a hardening accelerator, (F) a solvent, and (G) other additives. The following is a detailed description of each component contained in the resin composition.

<(A) Epoxy resin> The resin composition contains (A) epoxy resin as the (A) component. Examples of the epoxy resin (A) include bixylenol epoxy resins; bisphenol A epoxy resins; bisphenol F epoxy resins; bisphenol S epoxy resins; bisphenol AF epoxy resins; dicyclopentadiene epoxy resins; trisphenol epoxy resins; phenol novolac epoxy resins; glycidylamine epoxy resins; glycidyl ester epoxy resins; cresol novolac epoxy resins; biphenyl epoxy resins; chain aliphatic epoxy resins; epoxy resins having butylene; Epoxy resins with diene structure; alicyclic epoxy resins; heterocyclic epoxy resins; epoxy resins containing spiro rings; cyclohexane type epoxy resins; cyclohexanedimethanol type epoxy resins; trihydroxymethyl type epoxy resins; tetraphenylethane type epoxy resins; naphthyl ether type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, naphthol novolac type epoxy resins, and other epoxy resins containing condensed skeletons. The epoxy resins may be used alone or in combination of two or more. Among them, the epoxy resin (A) preferably includes an epoxy resin containing a condensed skeleton from the viewpoint of significantly obtaining the effects of the present invention.

The resin composition preferably includes an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin (A). From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio 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 component of the epoxy resin (A).

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

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin and epoxy resin having a butadiene structure are preferred, and alicyclic epoxy resin having an ester skeleton and naphthalene type epoxy resin 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 "EPICOTE" 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" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "EX-721" (glycidyl ester type epoxy resin) manufactured by NAGASE CHEM TEX; "CELLOXIDE "2021P" manufactured by DAICEL (epoxy resin with an ester skeleton); "PB-3600" manufactured by DAICEL (epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumitomo Metal Chemicals (liquid 1,4-glycidylcyclohexane type epoxy resins), etc. These may be used alone or in combination of two or more.

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 are bixylene 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, and more preferred are naphthalene 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 resin) 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" (dicyclopentadiene-based epoxy resin) manufactured by DIC Corporation; "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol phenolic varnish epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H" manufactured by Nippon Kayaku Co., Ltd., "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (naphthol type epoxy resin); "ESN485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (naphthol novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (xylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation "YX8800" manufactured by Mitsubishi Chemical (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical; "YL7760" manufactured by Mitsubishi Chemical (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical (solid bisphenol A type epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical (tetraphenylethane type epoxy resin), etc. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin (A), the mass ratio of the liquid epoxy resin: the solid epoxy resin is preferably 1:0.1 to 1:20, more preferably 1:1 to 1:10, and particularly preferably 1:1.5 to 1:5. By making the mass ratio of the liquid epoxy resin to the solid epoxy resin within this range, the desired effect of the present invention can be significantly obtained. Furthermore, when it is usually used in the form of a resin sheet, it also has moderate adhesiveness. And when it is usually used in the form of a resin sheet, it has sufficient flexibility and improved handling. Furthermore, a hardened material having sufficient fracture strength can usually be obtained.

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

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100-5000, more preferably 100-4000, and even more preferably 200-5000 in order to significantly obtain the desired effect of the present invention. The weight average molecular weight of the resin is a value converted to polystyrene measured by gel permeation chromatography (GPC).

(A) The content of the epoxy resin is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, based on the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, when the non-volatile components in the resin composition are set to 100% by mass. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, based on the viewpoint of significantly obtaining the expected effect of the present invention. In addition, in the present invention, the content of each component in the resin composition is the value when the non-volatile components in the resin composition are set to 100% by mass, unless otherwise specified.

<(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 the (B) component. The curing agent generally has the function of curing the resin composition by reacting with the (A) component, but in particular, by containing such a curing agent in the resin composition, in addition to the function of curving the resin composition by reacting with the (A) component, a cured product with suppressed warping can be obtained. The (B) component can be used alone or in combination of two or more.

Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnalidic anhydride, hydrogenated methylnalidic anhydride, trialkyltetrahydrophthalic anhydride, dodecylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, homotriac Pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonatetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene-maleic acid resin copolymerized with maleic acid, etc.

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

Examples of amine-based hardeners include hardeners having one or more amine groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of exerting the desired effect of the present invention. The amine-based hardener is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfonate, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonate, 3,3'-diaminodiphenylsulfonate, m-phenyldiamine, m-xylyldiamine, 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)benzidine, bis(4-aminophenoxy)phenyl)sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, and the like.

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

An example of a phenolic hardener is a hardener having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in one molecule. Among them, compounds having a hydroxyl group bonded to a benzene ring are preferred. Moreover, from the viewpoint of heat resistance and water resistance, a phenolic hardener having a novolac structure is preferred. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenolic hardener is preferred, and a phenolic hardener containing a triazine skeleton is more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenolic novolac hardener containing a triazine skeleton is preferred.

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", and "LA- "7054", "LA-1356", "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 remarkably obtaining the effect of the present invention, the content of the component (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, when the non-volatile components in the resin composition are set to 100% by mass.

When the number of epoxy groups of component (A) is set to 1, the number of active groups of component (B) is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, preferably 2 or less, more preferably 1.8 or less, and even more preferably 1.5 or less. Here, the so-called "number of epoxy groups of component (A)" is the total value of the mass of the non-volatile components of component (A) present in the resin composition divided by the value of the epoxy equivalent. And the so-called "number of active groups of component (B)" is the total value of the mass of the non-volatile components of component (B) present in the resin composition divided by the value of the active group equivalent. By setting the number of active groups of component (B) within the above range when the number of epoxy groups of component (A) is set to 1, the expected effect of the present invention can be significantly obtained.

<(C) Polyester polyol resin with aromatic structure> The resin composition contains (C) polyester polyol resin with aromatic structure as component (C). By containing component (C) in the resin composition, the stress of the cured product can be relieved, and as a result, a cured product with high bonding strength and suppressed warping of the cured product can be obtained. In addition, since component (C) can play a role in relieving stress, the thermal expansion coefficient (CTE) of the cured product can usually be reduced. Component (C) can be used alone or in combination of two or more.

The content of the component (C) is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more, and further preferably 5% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, from the viewpoint of obtaining a cured product having high bonding strength and suppressed warping of the cured product. From the viewpoint of obtaining a cured product having excellent bonding strength and thermal expansion coefficient, the upper limit is 20% by mass or less, preferably 15% by mass or less, further preferably 10% by mass or less, and further preferably 8% by mass or less.

From the viewpoint of suppressing the occurrence of warping of the cured product, improving the adhesion to the conductive layer such as copper foil, and further improving the hydrolyzability, the component (C) is preferably a resin having a structure derived from polyester and a structure derived from polyol. The resin can be obtained, for example, by reacting a polyol with a polycarboxylic acid. And as the component (C), it is preferred that either the structure derived from polyester or the structure derived from polyol has an aromatic structure. From the viewpoint of significantly obtaining the effect of the present invention, it is more preferred that either the structure derived from polyester or the structure derived from polyol has a bisphenol skeleton, and it is even more preferred that the structure derived from polyol has a bisphenol skeleton. The so-called aromatic structure is generally defined as an aromatic chemical structure, and also includes polycyclic aromatics and aromatic heterocycles. Examples of the bisphenol skeleton include a bisphenol A skeleton, a bisphenol B skeleton, a bisphenol C skeleton, and a bisphenol AF skeleton, and a bisphenol A skeleton is preferred.

From the viewpoint of improving the compatibility with the epoxy resin (A) and the adhesion to the copper foil, etc., the component (C) preferably has a molecular chain terminal of either a hydroxyl group or a carboxyl group. The number of hydroxyl groups and carboxyl groups contained in the component (C) is preferably 2 or more, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, and particularly preferably 2 per molecule.

From the viewpoint of significantly obtaining 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-} ).

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 having an alicyclic structure such as cyclohexanedimethanol; polyols having an aromatic structure such as bisphenol A and bisphenol F; and polyols having the aforementioned aromatic structures modified with alkylene oxide. Among them, polyols having an alicyclic structure, polyols having an aromatic structure, and polyols having an aromatic structure modified with alkylene oxide are preferred, and polyols having an aromatic structure modified with alkylene oxide are more preferred. One type of polyol may be used alone, or two or more types may be used in combination.

Examples of alkylene oxides used for modifying polyols 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.

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

Commercially available polyols may be used, and examples of commercially available polyols include "High Blocks MDB-561" manufactured by DIC Corporation.

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 naphthalenedicarboxylic acid; and anhydrides or esters thereof.

The polycarboxylic acid may be used alone or in combination of two or more, preferably aliphatic polycarboxylic acid. The content of aliphatic polycarboxylic acid is preferably 5 mol% or more, more preferably 10 mol% or more, and preferably 100 mol% or less in the total content of the polycarboxylic acid.

As one embodiment, aliphatic polycarboxylic acid and aromatic polycarboxylic acid are used in combination as polycarboxylic acid. The content ratio of aromatic polycarboxylic acid to aliphatic polycarboxylic acid (aromatic polycarboxylic acid/aliphatic polycarboxylic acid) is preferably 1/99 or more, more preferably 30/70 or more, and even more preferably 50/50 or more, and preferably 99/1 or less, more preferably 90/10 or less, and even more preferably 85/15 or less, on a molar basis. By setting the content ratio of aromatic polycarboxylic acid to aliphatic polycarboxylic acid within this range, the effect of the present invention can be significantly obtained.

The component (C) may contain an oxyalkylene unit having 4 or more carbon atoms to the extent that the purpose of the present invention is not impeded. 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 preferably 3% by mass or less, and particularly preferably 1% by mass or less.

The component (C) can be produced, for example, by reacting a polyol with a polycarboxylic acid. The reaction temperature is preferably 190°C or higher, more preferably 200°C or higher, preferably 250°C or lower, and more preferably 240°C or lower. The reaction time is preferably 1 hour or longer, and preferably 100 hours or shorter.

During the reaction, a catalyst may be used as needed. Examples of the catalyst include titanium-based catalysts such as tetraisopropyl titanium ester and tetrabutyl titanium ester; tin-based catalysts such as dibutyltin oxide; 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 viewpoint of effective 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.

The hydroxyl 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 preferably 50 mgKOH/g or less, 45 mgKOH/g or less, or 40 mgKOH/g or less, from the viewpoint of remarkably obtaining the effect of the present invention. The hydroxyl value can be measured by a method in accordance with JIS K0070.

Furthermore, the acid value of the component (C) is preferably 2 mgKOH/g or more, more preferably 4 mgKOH/g or more, and 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, and further 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 invention. The acid value can be measured by a method in accordance with JIS K0070.

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

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

The glass transition temperature of the component (C) is preferably -100°C or higher, more preferably -80°C or higher, and even more preferably -70°C or higher, and is preferably 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower, from the viewpoint of remarkably obtaining the effect of the present invention. The glass transition temperature is a value measured by DSC (differential scanning calorimetry).

<(D) Inorganic filler> The resin composition contains (D) inorganic filler. By containing (D) inorganic filler in the resin composition, a cured product with excellent thermal expansion coefficient can be obtained.

Inorganic compounds are used as materials for the inorganic filler. Examples of materials for the inorganic filler include silicon oxide, aluminum oxide, 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, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among them, silicon oxide and aluminum oxide are suitable, and silicon oxide is particularly preferred. Examples of silicon oxide include amorphous silicon oxide, molten silicon oxide, crystalline silicon oxide, synthetic silicon oxide, hollow silicon oxide, etc. And spherical silicon oxide is preferred as silicon oxide. (D) The inorganic filler may be used alone or in combination of two or more.

Examples of commercially available products of (D) inorganic fillers include "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; "SILFIL NSS-3N", "SILFIL NSS-4N", and "SILFIL NSS-5N" manufactured by Tokuyama; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by ADMATECHS; and the like.

(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, preferably 25 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less, from the viewpoint of significantly obtaining the desired effect of the present invention.

The average particle size of (D) inorganic fillers can be measured by laser diffraction/scattering method based on Mie scattering theory. Specifically, a laser diffraction particle size distribution measuring device can be used to make a particle size distribution of the inorganic filler based on volume, and the median diameter can be used for measurement. The measurement sample can be made by measuring 100 mg of inorganic filler and 10 g of methyl ethyl ketone in an ampoule and dispersing them ultrasonically for 10 minutes. The sample is measured using a laser diffraction particle size distribution measuring device, and the wavelength of the light source is set to blue and red. The volume-based particle size distribution of (D) inorganic fillers is measured by flow cell method, and the average particle size is calculated from the obtained particle size distribution as the median diameter. An example of a laser diffraction particle size distribution measuring device is "LA-960" manufactured by Horiba, Ltd.

(D) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 1.5 m ² /g or more, and particularly preferably 2 m 2 /g or more or 3 m ² /g or more, from the viewpoint of significantly obtaining the desired effect of the present invention. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 ^{m 2 /} g or less, or 40 m ² /g or less. The specific surface area can be obtained by adsorbing nitrogen on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH) according to the BET method, and calculating the specific surface area using the BET multi-point method.

From the viewpoint of improving moisture resistance and dispersibility, (D) inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, butylsilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organic silazane compounds, and titanium ester-based coupling agents. In addition, 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-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBM803" (3-butylpropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical, and "KBM573" (N-phenyl- 3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc.

The degree of surface treatment with the surface treatment agent is preferably limited to a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by weight of the inorganic filler is preferably treated with 0.2 to 5 parts by weight of the surface treatment agent, more preferably 0.2 to 3 parts by weight, and even more preferably 0.3 to 2 parts by weight.

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

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 a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, a carbon analyzer is used to measure the amount of carbon per unit surface area of the inorganic filler. As for the carbon analyzer, for example, the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

From the viewpoint of significantly achieving the desired effect of the present invention, the content of the (D) inorganic filler is preferably 60% by mass or more, more preferably 65% by mass or more, further preferably 70% by mass or more, 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, 90% by mass or less, when the non-volatile components in the resin composition are set to 100% by mass.

When the content of the component (D) is d1 and the content of the component (C) is c1, the ratio of d1/c1 is preferably 5 or more, more preferably 10 or more, and even more preferably 15 or more, and preferably 70 or less, and even more preferably 60 or less, and even more preferably 50 or less, 45 or less, 40 or less, or 35 or less, from the viewpoint of remarkably obtaining the effect of the present invention.

<(E) Hardening accelerator> The resin composition may further contain (E) a hardening accelerator as an optional component in addition to the above components. By containing (E) a hardening accelerator, the hardening time, etc. can be effectively adjusted.

Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferred. The hardening accelerators 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, butyltriphenylphosphonium thiocyanate, etc., preferably 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, 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.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2- -methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole 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-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl imidazole compounds such as imidazole, 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 curing accelerator, commercially available products may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation, "Curezol 2Mz", "2E4MZ", "C11Z", "C11Z-CN", "C11Z-CNS", "C11Z-A", "2MZ-OK", "2MA-OK", "2PHZ" and the like manufactured by Shikoku Chemical Industries, Ltd.

Examples of guanidine-based hardening accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 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, 1-(o-tolyl)biguanidine, etc., preferably 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of metal hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

(E) The content of the hardening accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and preferably 1.5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the viewpoint of remarkably obtaining the expected effect of the present invention, when the non-volatile component in the resin composition is set to 100% by mass.

<(F) Solvent> The resin composition may further contain any solvent as a volatile component. Examples of the solvent include organic solvents. Moreover, the solvent may be used alone or in combination of two or more in any proportion. The smaller the amount of solvent, the better. The amount of solvent relative to 100% by mass of the non-volatile components in the resin composition is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, and particularly preferably contains no solvent (0% by mass). Moreover, when the amount of such solvent is small, the resin composition may also be in a paste state. The viscosity of the paste resin composition at 25°C is preferably in the range of 20Pa·s~1000Pa·s.

<(G) Other additives> In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Examples of such additives include thermoplastic resins; hardeners other than component (B); organic fillers; resin additives such as thickeners, defoamers, leveling agents, adhesion agents, flame retardants, etc. These additives may be used alone or in combination of two or more.

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 is added to the formulation components as needed, and the mixture is mixed and dispersed using a rotary mixer.

<Physical properties and uses of resin composition> The cured product of the resin composition heat-cured at 180°C for 90 minutes shows excellent bonding strength. The bonding strength can be represented by shear strength, for example. Therefore, the aforementioned cured product usually leads to an insulating layer or sealing layer with excellent shear strength. The shear strength is preferably 2kgf/ ^mm2 or more. The evaluation of shear strength can be measured according to the method described in the embodiment described below.

The resin composition is heat cured at 190°C for 90 minutes and the cured product generally shows a low coefficient of thermal expansion (CTE). Therefore, the cured product results in an insulating layer or sealing layer with a low coefficient of thermal expansion. The coefficient of thermal expansion (CTE) is preferably less than 13 ppm/°C. The evaluation of the coefficient of thermal expansion can be measured according to the method described in the embodiment described below.

The cured product obtained by heat curing the resin composition at 190°C for 90 minutes shows a characteristic of suppressed warping. Therefore, the cured product results in an insulating layer or a sealing layer with suppressed warping. Specifically, a resin composition is compression-molded on a silicon wafer to obtain a resin composition layer. A sample substrate is obtained by heat 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, a standard of the Electronics and Information Technology Industry Association. The aforementioned warping amount does not reach 2 mm. The warping amount measurement details can be measured according to the method described in the embodiment described later.

Since the resin composition has the above-mentioned properties, it can be suitably used as a resin composition for sealing electronic devices such as organic EL devices or semiconductors (resin composition for sealing), particularly as a resin composition for sealing semiconductors (resin composition for semiconductor sealing), and more preferably as a resin composition for sealing semiconductor chips (resin composition for semiconductor chip sealing). In addition to the sealing purpose, the resin composition can be used as a resin composition for insulating purposes such as 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 insulating layer of semiconductor chip package) and a resin composition for forming an insulating layer of a circuit substrate (including a printed wiring board) (resin composition for insulating layer of a circuit substrate).

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), fan-in PLP, etc.

Furthermore, the resin composition can be used as an underfill material, for example, as a material for MUF (Molding Under Filling) 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 lamination materials, solder resists, die bonding materials, via-filling resins, component embedding resins, and the like.

[Resin sheet] The resin sheet of the present invention has a support and a resin composition layer disposed on the support. The resin composition layer is a layer including the resin composition of the present invention, and is usually formed of a resin composition.

The thickness of the resin composition layer is preferably 600 μm or less, 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 from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is not particularly limited, but is, for example, 1 μm or more, 5 μm or more, 10 μm or more, etc.

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

When a film made of a plastic material is used as a 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 polyolefin; triacetyl cellulose (hereinafter sometimes referred to as "TAC"); polyether sulfide (hereinafter sometimes referred to as "PES"); polyether ketone; polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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 a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

The support body may also be subjected to a treatment such as a matte treatment, a corona treatment, an antistatic treatment, etc. on the surface that is bonded to the resin composition layer.

Furthermore, as a support body, a support body with a release layer having a release layer on the surface bonded to the resin composition layer can also be used. Examples of release agents used in the release layer of the support body with a release layer include at least one release agent selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Examples of commercially available release agents include alkyd resin release agents such as "SK-1", "AL-5", and "AL-7" manufactured by LINTEC. Examples of the support body with a release layer include "LUMIRROR T60" manufactured by Toray Industries, "PUREX" manufactured by Teijin, and "UNIPEEL" manufactured by UNITIKA.

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 support with a release layer is preferably in the above range.

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

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

Drying can be carried out by known methods such as heating and hot air blowing. The drying condition is to dry until the organic solvent content in the resin composition layer is usually 10 mass% or less, preferably 5 mass% or less. Although it varies with the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30 mass% to 60 mass% of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

The resin sheet may include any layer other than the support and the resin component layer as required. For example, in the resin sheet, a protective film depending on the support may be provided on the surface of the resin component 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 may be, for example, 1 μm to 40 μm. The protective film can inhibit dirt from adhering to or scratching the surface of the resin component layer. When the resin sheet has a protective film, the resin sheet can be used by removing the protective film. The resin sheet can also be rolled into a roll for storage.

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

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

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

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 preferably used to form an insulation layer of a circuit substrate such as a printed wiring board.

[Circuit board] The circuit board of the present invention includes a cured layer formed by a cured product of the resin composition of the present invention. The cured layer may be an insulating layer or a sealing layer. The circuit board may be manufactured by a manufacturing method including, for example, 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. Examples of the substrate include glass epoxy substrates, metal substrates (stainless steel or cold-pressed rolled steel (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. The substrate may also have a metal layer such as copper foil on its surface as part of the substrate. For example, a substrate having a first metal layer and a second metal layer that can be peeled off on both surfaces may be used. When using such substrates, a conductive layer that serves as a wiring layer that can function as circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. Examples of the material of the metal layer include copper foil, copper foil with a carrier, and the material of the conductor layer described below, and copper foil is preferred. Commercially available products can be used as the substrate having the metal layer, for example, an ultra-thin copper foil "Micro Thin" with a carrier copper foil manufactured by Mitsui Mining & Co., Ltd.

Furthermore, a conductive layer may be formed on the surface of one or both of the substrates. In the following description, a component including a substrate and a conductive layer formed on the surface of the substrate is sometimes appropriately referred to as a "substrate with a wiring layer". Examples of conductive materials contained in the conductive layer include materials including one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductive material, a single metal may be used, 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 alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoint of wide availability, 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 nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy as an alloy are preferred. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal, and nickel-chromium alloy are more preferred, and copper as a single metal is particularly preferred.

The conductor layer may also be patterned, for example, in order to function as a wiring layer. In this case, the line (circuit width)/spacing (spacing between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (i.e., spacing is 40 μm or less), more preferably 10/10 μm or less, still more preferably 5/5 μm or less, still more preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The spacing does not necessarily have to be the same throughout the conductor layer. The minimum spacing of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

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

The conductive layer can be formed by a method comprising the following steps: a step of laminating a dry film (photosensitive resist film) on a substrate; a step of exposing and developing the dry film under specific conditions using a photomask to form a pattern to obtain a patterned dry film; a step of forming a conductive layer by a coating method such as an electrolytic coating method using the developed patterned dry film as a coating mask; and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film formed of a photoresist composition can be used, for example, a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. The lamination conditions of the substrate and the dry film are the same as the lamination conditions of the substrate and the resin sheet described later. The stripping of the dry film can be carried out using an alkaline stripping liquid such as sodium hydroxide solution.

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

The resin composition layer is formed, for example, by laminating a resin sheet and a substrate. The lamination can be performed, for example, by heat-pressing the resin sheet to the substrate from the side of the support so that the resin composition layer is attached to the substrate. Examples of the member for heat-pressing the resin sheet to the substrate (hereinafter sometimes referred to as the "heat-pressing member") include, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller, etc.). In addition, the preferred heat-pressing member is not directly pressed on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber in a manner that allows the resin sheet to fully follow the surface irregularities of the substrate.

The lamination of the substrate and the resin sheet can also be performed by, for example, 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. Lamination is preferably performed under reduced pressure conditions with a pressure of less than 13hPa.

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

The resin composition layer can be formed by, for example, compression molding. The specific operation of the compression molding method is, for example, preparing an upper mold and a lower mold as a mold. Applying the resin composition to the substrate. Installing the substrate coated with the resin composition to the lower mold. Then, the upper mold and the lower mold are molded together, and heat and pressure are applied to the resin composition for compression molding.

The specific operation of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed on the lower mold. A base material is mounted on the upper mold. Then, the upper mold and the lower mold are clamped together in such a manner that the resin composition placed on the lower mold is in contact with the base material mounted on the upper mold, and heat and pressure are applied to perform compression molding.

The molding conditions in the compression molding method vary with the composition of the resin composition. The mold temperature during molding is preferably a temperature that allows the resin composition to exhibit excellent compression molding properties, for example, preferably 80°C or higher, more preferably 100°C or higher, more preferably 120°C or higher, preferably 200°C or lower, more preferably 170°C or lower, and more preferably 150°C or lower. In addition, the pressure applied during molding is preferably 1MPa or higher, more preferably 3MPa or higher, more preferably 5MPa or higher, preferably 50MPa or lower, more preferably 30MPa or lower, and more preferably 20MPa or lower. 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, particularly preferably 20 minutes or less. Usually, after the resin composition layer is formed, the mold is removed. The mold can be removed before the resin composition layer is thermally cured, or after the thermal curing.

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

Before the resin composition layer is heat-hardened, the resin composition layer may be preheated at a temperature lower than the hardening temperature. For example, before the resin composition layer is heat-hardened, the resin composition layer may be preheated at a temperature of usually 50°C or higher and lower than 120°C (preferably 60°C or higher and 110°C or lower, and more preferably 70°C or higher and 100°C or lower) for usually 5 minutes or more (preferably 5 minutes to 150 minutes, and more preferably 15 minutes to 120 minutes).

As described above, a circuit substrate having an insulating layer can be manufactured. In addition, the manufacturing method of the circuit substrate can further include any steps. For example, when a circuit substrate is manufactured using a resin sheet, the manufacturing method of the circuit substrate can include the step of peeling off the support body of the resin sheet. The support body can be peeled off before the resin component layer is thermally cured, and can also be peeled off after the resin component layer is thermally cured.

The manufacturing method of the circuit substrate may include a step of grinding the surface of the insulating layer after forming the insulating layer. The grinding method is not particularly limited. 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 also include, for example, the step (3) of connecting the conductor layer between layers, that is, the step of perforating the insulating layer. In this way, holes such as perforations and through holes can be formed in the insulating layer. Examples of the method of forming the perforations include laser irradiation, etching, mechanical drilling, etc. The size or shape of the perforations can be appropriately determined according to the design of the circuit substrate. In addition, step (3) can also be performed by grinding or grinding the insulating layer to connect between layers.

After the through-hole is formed, it is preferred to perform a step of removing the slag in the through-hole. This step is sometimes called a deslagging step. For example, when a conductive layer is formed on an insulating layer by a coating step, a wet deslagging treatment may be performed on the through-hole. Also, when a conductive layer is formed on an insulating layer by a sputtering step, a dry deslagging step such as a plasma treatment step may be performed. Furthermore, the insulating layer may also be roughened by a deslagging step.

Furthermore, before forming the conductive layer on the insulating layer, the insulating layer may be subjected to a roughening treatment. According to the roughening treatment, the surface of the insulating layer including the through-holes can be generally roughened. The roughening treatment may be performed by either a dry roughening treatment or a wet roughening treatment. An example of a dry roughening treatment is a plasma treatment. Another example of a wet roughening treatment is a method of sequentially performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing agent.

After the perforations are formed, a conductive layer can be formed on the insulating layer. By forming a conductive layer at the location where the perforations are formed, the newly formed conductive layer is connected to the conductive layer on the surface of the substrate to achieve inter-layer connection. Examples of methods for forming the conductive layer include plating, sputtering, evaporation, etc., among which plating is preferred. In a preferred embodiment, plating is performed on the surface of the insulating layer by an appropriate method such as a semi-additive method or a full-additive method to form a conductive layer with a desired wiring pattern. Furthermore, when the support in the resin sheet is a metal foil, a conductive layer with a desired wiring pattern can be formed by a subtractive method. The material of the conductive layer to be formed can be a single metal or an alloy. The conductive layer may have a single-layer structure or a multi-layer structure including two or more layers made 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 coating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed coating seed layer corresponding to the desired wiring pattern to expose a portion of the coating seed layer. After an electrolytic coating layer is formed on the exposed coating seed layer by electrolytic plating, the mask pattern is removed. Subsequently, the unnecessary coating seed layer is removed by etching or the like, and a conductive layer having the desired wiring pattern can be formed. Furthermore, when forming the conductive layer, the dry film used to form the mask pattern is the same as the above-mentioned dry film.

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

[Semiconductor chip package] The semiconductor chip package of the 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.

The bonding conditions between the circuit board and the semiconductor chip can be any conditions that can connect the terminal electrodes of the semiconductor chip to the circuit wiring conductors of the circuit board. For example, the conditions used in flip-chip mounting of semiconductor chips can be used. And for example, the semiconductor chip and the circuit board can be bonded via an insulating adhesive.

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

Another example of the bonding method is to reflow the semiconductor chip to the circuit board for bonding. The reflow condition can be set in the range of 120°C to 300°C.

After the semiconductor chip is bonded to the circuit substrate, the semiconductor chip may be filled with a mold underfill material. The mold underfill material may be the resin composition or the resin composition layer of the resin sheet.

The semiconductor chip package of the second embodiment of the present invention comprises a semiconductor chip and a hardened material of the aforementioned resin composition for sealing the semiconductor chip. In such semiconductor chip package, the hardened material of the resin composition usually functions as a sealing layer. The semiconductor chip package of the second embodiment is exemplified by a fan-out WLP.

The manufacturing method of the semiconductor chip package such as fan-out WLP includes: (A) a step of laminating a temporary fixing film on a substrate, (B) a step of temporarily fixing a semiconductor chip on the temporary fixing film, (C) laminating a resin composition layer of the resin sheet of the present invention on the semiconductor chip, or coating the resin composition of the present invention on the semiconductor chip and thermally curing it to form a sealed (D) a step of peeling off the substrate and the temporary fixing film from the semiconductor chip, (E) a step of 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 off, (F) a step of forming a conductor layer (redistribution layer) on the redistribution layer (insulating layer), and (G) a step of forming a solder resist layer on the conductor layer. In addition, the manufacturing method of the semiconductor chip package may also include: (H) a step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages for singulation.

The details of the manufacturing method of these semiconductor packages can be found in paragraphs 0066 to 0081 of International Publication No. 2016/035577, the contents of which are incorporated into this specification.

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

[Semiconductor device] Examples of semiconductor devices in which the semiconductor chip package is mounted include various semiconductor devices used in electrical products (such as computers, mobile phones, smart phones, tablet devices, wearable devices, digital cameras, medical devices, and televisions, etc.) and vehicles (such as motorcycles, cars, trains, ships, and airplanes, etc.). [Example]

The present invention is specifically described below by way of examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating amounts, unless otherwise specified, mean "parts by mass" and "% by mass", respectively. The operations described below are performed at room temperature and pressure unless otherwise specified.

The silicon oxide A, silicon oxide B and aluminum oxide A used in the examples and comparative examples are as follows. Silicon oxide A: average particle size 1.8 μm, specific surface area 3.5 m ² /g, silicon oxide surface treated with N-phenyl-3-aminopropyl trimethoxysilane ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.). Silicon oxide B: average particle size 3.2 μm, specific surface area 4.6 m ² /g, silicon oxide surface treated with 3-glycidyloxypropyl trimethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.). Alumina A: average particle size 6.2 μm, specific surface area 1.7 m ² /g, aluminum oxide surface treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.).

<Synthesis Example 1: Synthesis of Polyester Polyol Resin A with Aromatic Structure> Into the reaction apparatus, 779.1 parts by mass of bisphenol A type glycol ether (High Blocks MDB-561, manufactured by DIC Corporation), 132.9 parts by mass of isophthalic acid, and 40.4 parts by mass of sebacic acid were fed, and the temperature was raised and stirred. Then, after the internal temperature rose to 230°C, 0.10 parts by mass of tetraisopropyl titanium ester was fed, and the reaction was carried out at 230°C for 24 hours to synthesize the polyester polyol resin A with aromatic structure. The obtained polyester polyol resin A with aromatic structure has OH groups at both ends, its hydroxyl value is 36.9 mgKOH/g, the number average molecular weight is 3040, the glass transition temperature is -14°C, and the viscosity at 75°C is 9 Pa·s.

<Synthesis Example 2: Synthesis of Polyester Polyol Resin B with Aromatic Structure> 596.8 parts by mass of bisphenol A type glycol ether (High Blocks MDB-561, manufactured by DIC Corporation) and 257.4 parts by mass of sebacic acid were fed into the reaction apparatus, and the temperature was raised and stirred. Then, after the internal temperature rose to 230°C, 0.10 parts by mass of tetraisopropyl titanium ester was fed, and the reaction was carried out at 230°C for 24 hours to synthesize the polyester polyol resin B with aromatic structure. The obtained polyester polyol resin B with aromatic structure has -COOH groups at both ends, an acid 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.

<Example 1> Using a mixer, 6.6 parts of an epoxy resin ("CEL2021P" manufactured by DAICEL, epoxy equivalent 136 g/eq.), 8 parts of a naphthalene epoxy resin ("HP4032D" manufactured by DIC, epoxy equivalent 142 g/eq.), 0.5 parts of an amine curing agent ("KYAHARD A-A" manufactured by Nippon Kayaku Co., Ltd.), 2.5 parts of a polyester polyol resin A having an aromatic structure synthesized in Synthesis Example 1, 80 parts of silicon oxide A, and 0.4 parts of a curing accelerator ("2MA-OK" manufactured by Shikoku Chemical Co., Ltd.) were uniformly dispersed to obtain a resin composition 1.

<Example 2> In Example 1, 0.5 parts of polyester polyol resin A having an aromatic structure is replaced with 0.5 parts of polyester polyol resin B having an aromatic structure. Resin composition 2 is prepared in the same manner as in Example 1 except for the above matters.

<Example 3> Using a mixer, 3 parts of an epoxy resin ("CEL2021P" manufactured by DAICEL, epoxy equivalent 136 g/eq.), 3 parts of a naphthalene epoxy resin ("HP4032D" manufactured by DIC, epoxy equivalent 142 g/eq.), 10 parts of an acid anhydride curing agent ("MH-700" manufactured by Shin Nippon Chemical Co., Ltd.), 4 parts of the polyester polyol resin A having an aromatic structure synthesized in Synthesis Example 1, 100 parts of silicon oxide A, and 0.5 parts of a curing accelerator ("2MA-OK" manufactured by Shikoku Chemical Co., Ltd.) were uniformly dispersed to obtain a resin composition 3.

<Example 4> In Example 3, 4 parts of polyester polyol resin A with an aromatic structure are changed to 8 parts of polyester polyol resin B with an aromatic structure, and 100 parts of silicon oxide A are changed to 130 parts of aluminum oxide A. Except for the above matters, resin composition 4 is prepared in the same manner as in Example 3.

<Example 5> Using a mixer, 7 parts of an epoxy resin ("CEL2021P" manufactured by DAICEL, epoxy equivalent 136 g/eq.), 8 parts of a naphthalene epoxy resin ("HP4032D" manufactured by DIC, epoxy equivalent 142 g/eq.), 1 part of a phenolic curing agent (2,2-diallylbisphenol A), 2 parts of a polyester polyol resin A having an aromatic structure synthesized in Synthesis Example 1, 70 parts of silicon oxide A, and 0.4 parts of a curing accelerator ("2MA-OK" manufactured by Shikoku Chemical Co., Ltd.) were uniformly dispersed to obtain a resin composition 5.

<Comparative Example 1> In Example 2, 2.5 parts of polyester polyol resin A having an aromatic structure are not used. Resin composition 6 is prepared in the same manner as in Example 2 except for the above matters.

<Comparative Example 2> In Example 3, the amount of polyester polyol resin A having an aromatic structure was changed from 4 parts to 0.5 parts. Resin composition 7 was prepared in the same manner as in Example 3 except for the above matters.

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

<Evaluation of shear strength> On a silicon wafer coated with polyimide, a silicone rubber frame with a diameter of 4mm was hollowed out, and the resin compositions 1 to 8 prepared in the embodiment and the comparative example were filled into a cylindrical shape with a height of 5mm. After heating at 180°C for 90 minutes, the silicone rubber frame was removed to prepare a test piece made of the cured resin composition. The shear strength of the interface between polyimide and the test piece was measured using an adhesion tester (Series 4000 manufactured by Dage) with the head position at a distance of 1mm from the substrate and a head speed of 700μm/s. The test was performed 5 times, and the average value was used for evaluation according to the following criteria. ○: 2kgf/ ^mm2 or more ×: less than 2kgf/ ^mm2

<Measurement of warp> On a 12-inch silicon wafer, the resin composition prepared in the embodiment and the comparative example was compression molded using a compression molding device (mold temperature: 130°C, pressure: 6MPa, curing time: 10 minutes) to form a resin composition layer with a thickness of 300μm. Subsequently, the resin composition layer was thermally cured by heating at 180°C for 90 minutes. In this way, a sample substrate including a silicon wafer and a cured layer of the resin composition was obtained. The warp of the aforementioned sample substrate at 25°C was measured using a shadow overlay measuring device (Akorometrix "ThermoireAXP"). The measurement is carried out in accordance with the JEITA EDX-7311-24 standard of the Electronics and Information Technology Industry Association. Specifically, the virtual plane calculated by the least square method of all the data on the substrate surface of the measurement area is used as the reference plane, and the difference between the minimum and maximum values in the vertical direction from the reference plane is calculated as the warp amount. The warp amount less than 2mm is evaluated as "○", and more than 2mm is evaluated as "×".

<Determination of coefficient of thermal expansion (CTE)> On a 12-inch silicon wafer that had been subjected to demolding, the resin compositions 1 to 8 prepared in the embodiment and the comparative example were compression molded using a compression molding device (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes) to form a resin composition layer with a thickness of 300 μm. Subsequently, the resin composition layer was peeled off from the silicon wafer that had been subjected to demolding, and the resin composition layer was heated at 180°C for 90 minutes to thermally cure the resin composition layer to prepare a hardened sample. The hardened sample was cut into 5 mm wide and 15 mm long pieces to obtain test pieces. For the test piece, a thermomechanical analysis was performed using a thermomechanical analysis device ("ThermoPlus TMA8310" manufactured by RIGAKU) using the tensile weight method. Specifically, after the test piece was mounted in the aforementioned thermomechanical analysis device, two measurements were performed consecutively under the measurement conditions of a load of 1g and a heating rate of 5°C/min. Then, in the second measurement, the thermal expansion coefficient (ppm/°C) in the plane direction in the range of 25°C to 150°C was calculated and evaluated using the following criteria. ○: Less than 13ppm/°C ×: 13ppm/°C or more

In Examples 1 to 5, even when the component (E) was not included, the results were confirmed to be the same as those of the above-mentioned Examples, although there were differences in degree.

Claims (12)

A resin composition comprising (A) an 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) an inorganic filler, wherein the content of component (A) is 1% by mass or more and 30% by mass or less when the non-volatile components in the resin composition are set to 100% by mass, the content of component (C) is 2% by mass or more and 20% by mass or less when the non-volatile components in the resin composition are set to 100% by mass, and the content of component (D) is 60% by mass or more and 95% by mass or less when the non-volatile components in the resin composition are set to 100% by mass. The resin composition of claim 1, wherein component (A) comprises a condensed ring skeleton. The resin composition of claim 1, wherein the terminal of component (C) is either a hydroxyl group or a carboxyl group. The resin composition of claim 1, wherein component (C) is a resin having a structure derived from polyester and a structure derived from polyol. The resin composition of claim 4, wherein the structure derived from the polyol includes any one of an ethylene oxide structure, a propylene oxide structure, and a butylene oxide structure. The resin composition of claim 1, wherein component (C) has a bisphenol skeleton. The resin composition of claim 1, wherein c1 is the content of component (C) based on 100 mass % of nonvolatile components in the resin composition, and d1 is the content of component (D) based on 100 mass % of nonvolatile components in the resin composition, and d1/c1 is 5 or more and 70 or less. The resin composition of claim 1 is used as a sealing layer. A resin sheet comprises a support and a resin composition layer comprising the resin composition of any one of claims 1 to 8 disposed on the support. A circuit substrate comprising a cured material layer formed from a cured product of the resin composition of any one of claims 1 to 8. A semiconductor chip package comprises a circuit substrate as claimed in claim 10 and a semiconductor chip mounted on the circuit substrate. A semiconductor chip package comprising a semiconductor chip sealed by a resin composition as described in any one of claims 1 to 8 or a resin sheet as described in claim 9.