TWI884185B - Resin composition - Google Patents

Abstract

The subject of the present invention is to provide a resin composition that can suppress the generation of flow marks and warping after molding and can obtain a cured product with excellent heat-peel tape adhesion. The resin composition of the present invention, which is a means for solving the problem, is a resin composition comprising (A) a hardener and (B) an inorganic filler, wherein the component (A) comprises a hydroxyl-containing siloxane compound (A-1), and when the non-volatile components other than the component (B) in the resin composition are set to 100% by mass, the content of the component (A-1) is 0.5% by mass or more and less than 5% by mass, and when all the non-volatile components in the resin composition are set to 100% by mass, the content of the component (B) is 60% by mass or more.

Description

Resin composition

The present invention relates to a resin composition containing an inorganic filler and further to a cured product, a resin sheet, a circuit board, a semiconductor chip package and a semiconductor device obtained by using the resin composition.

In recent years, the demand for small and high-function electronic devices such as smart phones and tablet devices has been increasing. As a result, the sealing materials used in semiconductor chip packages used in these small electronic devices are required to have higher functionality. As such sealing materials, those formed by curing a resin composition are known (Patent Document 1).

In recent years, in particular, there has been a demand to thin the insulating layer or sealing material used in semiconductor chip packages. However, when the insulating layer or sealing layer is thinned, it tends to warp. As a method of suppressing warp, there is a known method of adding an epoxy-modified siloxane that can relieve stress to a resin composition (Patent Document 2). [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2017-008312 [Patent Document 2] Japanese Patent Publication No. 2018-172599

[The problem that the invention wants to solve]

However, when epoxy-modified siloxane is added to a resin composition, the following problems occur: the adhesion to the heat release tape used in the semiconductor chip package manufacturing process is reduced; and flow marks are easily generated after molding. Therefore, a resin composition is required that can not only suppress warping, but also suppress the generation of flow marks after molding, and further, can obtain a cured product with excellent heat release tape adhesion.

Therefore, the subject of the present invention is to provide a resin composition that can suppress the generation of flow marks and warping after molding, and can obtain a cured product with excellent heat-peel tape adhesion. [Means for solving the problem]

In order to achieve the subject of the present invention, the inventors of the present invention have conducted in-depth research and found that: "By using a resin composition containing (A-1) a hydroxyl-containing siloxane compound and (B) an inorganic filler in a specified ratio, the generation of flow marks and warping after molding can be suppressed, and a cured product with excellent heat-peel tape adhesion can be obtained.", thereby completing the present invention.

That is, the present invention includes the following contents. [1]. A resin composition comprising (A) a curing agent and (B) an inorganic filler, wherein the component (A) comprises (A-1) a hydroxyl-containing siloxane compound, when the non-volatile components other than the component (B) in the resin composition are taken as 100% by mass, the content of the component (A-1) is 0.5% by mass or more and less than 5% by mass, when the total non-volatile components in the resin composition are taken as 100% by mass, the content of the component (B) is 60% by mass or more. [2]. The resin composition as described in [1] above, wherein the component (A-1) is a phenolic hydroxyl-containing siloxane compound. [3]. The resin composition of [1] or [2] above, wherein the component (A-1) has a chain siloxane skeleton. [4]. The resin composition of any one of [1] to [3] above, wherein the hydroxyl value of the component (A-1) is 120 mgKOH/g or less. [5]. The resin composition of any one of [1] to [4] above, wherein the component (A) further comprises a hardener selected from a phenolic hardener, a naphthol hardener, an amine hardener, an active ester hardener, and an acid anhydride hardener. [6]. The resin composition of any one of [1] to [5] above, wherein the content of the component (A-1) is 3% to 20% by mass when the total amount of the component (A) is 100% by mass. [7]. The resin composition of any one of [1] to [6] above, wherein the component (B) is silicon dioxide. [8]. The resin composition of any one of [1] to [7] above, wherein the content of the component (B) is 70% by mass or more, based on 100% by mass of all non-volatile components in the resin composition. [9]. The resin composition of [8] above, wherein the content of the component (B) is 80% by mass or more, based on 100% by mass of all non-volatile components in the resin composition. [10]. The resin composition of any one of [1] to [9] above, wherein the content mass ratio of the component (B) to the component (A-1) (component (B)/component (A-1)) is 50 to 1,000. [11]. A resin composition as described in any one of [1] to [10] above, further comprising (C) an epoxy resin. [12]. A resin composition as described in any one of [1] to [11] above, used to form an insulating layer of a semiconductor chip package. [13]. A resin composition as described in any one of [1] to [11] above, used to form an insulating layer of a circuit board. [14]. A resin composition as described in any one of [1] to [11] above, used to seal a semiconductor chip in a semiconductor chip package. [15]. A cured product obtained from a resin composition as described in any one of [1] to [14] above. [16]. A resin sheet comprising a support and a resin composition layer disposed on the support, wherein the resin composition layer comprises the resin composition of any one of [1] to [14]. [17]. A circuit substrate comprising an insulating layer formed by a hardener, wherein the hardener is a hardener obtained from the resin composition of any one of [1] to [14]. [18]. A semiconductor chip package comprising the circuit substrate of [17] and a semiconductor chip mounted on the circuit substrate. [19]. A semiconductor chip package comprising a semiconductor chip and a hardener for sealing the semiconductor chip, wherein the hardener is a hardener obtained from the resin composition of any one of [1] to [14]. [20]. A semiconductor device having the semiconductor chip package of [18] or [19] above. [Effect of the invention]

The resin composition of the present invention can suppress the generation of flow marks and warping after molding, and can obtain a cured product having excellent heat-peel tape adhesion.

[Best Mode for Carrying Out the Invention]

The present invention is described in detail below according to its suitable embodiments. 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.

<Resin composition> The resin composition of the present invention comprises (A) a curing agent and (B) an inorganic filler, wherein the component (A) comprises (A-1) a hydroxyl-containing siloxane compound, and when the non-volatile components other than the component (B) in the resin composition are set to 100% by mass, the content of the component (A-1) is 0.5% by mass or more and less than 5% by mass, and when the total non-volatile components in the resin composition are set to 100% by mass, the content of the component (B) is 60% by mass or more. By using such a resin composition, the generation of flow marks and warping after molding can be suppressed, and a cured product having excellent heat-peel tape adhesion can be obtained.

The resin composition of the present invention may further include (C) epoxy resin, (D) curing accelerator, (E) other additives and (F) organic solvent in addition to (A) hardener and (B) inorganic filler. The components included in the resin composition are described in detail below.

<(A) Hardener> The resin composition of the present invention includes (A) hardener. (A) Hardener has the function of hardening (C) epoxy resin. (C) Epoxy resin, which is the hardening target of (A) hardener, may be included in the resin composition of the present invention, or may be separately mixed with the resin composition of the present invention before hardening.

The content of the (A) hardener in the resin composition is not particularly limited, but when the non-volatile components other than the (B) inorganic filler in the resin composition are taken as 100 mass%, it is, for example, 100 mass% or less, 95 mass% or less, 85 mass% or less, preferably 75 mass% or less, 70 mass% or less, further preferably 60 mass% or less, 55 mass% or less, more preferably 50 mass% or less, 45 mass% or less, and particularly preferably 42 mass% or less, 40 mass% or less. The lower limit of the content of the (A) hardener in the resin composition is not particularly limited, but when the non-volatile components other than the (B) inorganic filler in the resin composition are taken as 100 mass%, it is preferably 0.5 mass% or more, 1 mass% or more, 5 mass% or more, 10 mass% or more, more preferably 15 mass% or more, 20 mass% or more, more preferably 25 mass% or more, 30 mass% or more, and particularly preferably 35 mass% or more, 37 mass% or more.

<(A-1) Hydroxyl-containing siloxane compound> (A) The curing agent includes (A-1) a hydroxyl-containing siloxane compound. The so-called (A-1) hydroxyl-containing siloxane compound refers to a compound having one or more (preferably two or more) hydroxyl groups and one or more (preferably two or more, particularly preferably two or more repeated and continuous) siloxane (Si-O-Si) bonds.

The hydroxyl group-containing siloxane compound (A-1) may be a siloxane compound having a cyclic siloxane skeleton or a siloxane compound having a chain siloxane skeleton, and is preferably a siloxane compound having a chain siloxane skeleton.

The number of hydroxyl groups in the hydroxyl group-containing siloxane compound (A-1) is not particularly limited, but is preferably 10 or less, and more preferably 5 or less, in one molecule. When the hydroxyl group-containing siloxane compound (A-1) is a hydroxyl group-containing chain siloxane compound, it may be a side chain type having a hydroxyl group on the side chain, a dual terminal type having a hydroxyl group on both ends, or a side chain terminal type having a hydroxyl group on both the side chain and the terminal.

The number of silicon atoms forming siloxane bonds in the hydroxyl group-containing siloxane compound (A-1) is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and particularly preferably 5 or more in one molecule as a lower limit, and is preferably 2,000 or less, more preferably 1,000 or less, and particularly preferably 500 or less as an upper limit.

All the substitutable sites of the silicon atom in the hydroxyl-containing siloxane compound (A-1) which do not participate in the formation of siloxane bonds are preferably substituted with a monovalent organic group which may or may not have a hydroxyl group, and more preferably substituted with an optionally substituted monovalent hydrocarbon group which may or may not have a hydroxyl group.

(A-1) The hydroxyl group-containing siloxane compound is preferably a siloxane compound represented by formula (1).

[In the formula, at least two of the 2n+2 R ^1s and the 2 R ^2s independently represent an optionally substituted monovalent hydrocarbon group having one or more hydroxyl groups, and the others independently represent an optionally substituted monovalent hydrocarbon group; or, at least two of the 2n+2 R ^1s independently represent an optionally substituted monovalent hydrocarbon group having one or more hydroxyl groups, and the others independently represent an optionally substituted monovalent hydrocarbon group, and the two R ^2s together show one -O- and are bonded to each other to form a cyclic siloxane skeleton. n represents an integer greater than 2].

The "monovalent alkyl group" may be, for example, an alkyl group, an alkenyl group, an aryl group or a combination thereof. Examples of the combination include, but are not particularly limited to, an aryl group substituted with an aryl group, an alkenyl group and/or an alkyl group; an alkyl group substituted with an aryl group; and an alkenyl group substituted with an aryl group.

The so-called "monovalent alkyl group optionally substituted with one or more hydroxyl groups" means that the group is a monovalent alkyl group which may have one or more arbitrary substituents and has at least one hydroxyl group. The so-called "monovalent alkyl group optionally substituted" means a monovalent alkyl group which may have one or more arbitrary substituents (however, in order to distinguish it from "monovalent alkyl group optionally substituted with one or more hydroxyl groups", it means not having a hydroxyl group).

The so-called "alkyl" refers to a straight chain, branched chain and/or cyclic monovalent aliphatic saturated hydrocarbon group. The "alkyl" is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the "alkyl" include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, and the like.

The so-called "alkenyl" refers to a straight chain, branched chain and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The "alkenyl" is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. Examples of the "alkenyl" include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, and 2-cyclohexenyl.

The so-called "aryl" refers to a monovalent aromatic hydrocarbon group. The "aryl" is preferably an aryl group having 6 to 10 carbon atoms. Examples of the "aryl" include phenyl, 1-naphthyl, 2-naphthyl, and the like.

The optional substituent in the "optionally substituted monovalent alkyl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, a nitro group, an alkyl-oxy group, a mono- or di-(alkyl)-amino group, an alkyl-carbonyl group, an alkyl-oxy-carbonyl group, a mono- or di-(alkyl)-amino-carbonyl group, an alkyl-carbonyl-oxy group, a mono- or di-(alkyl-carbonyl)-amino group, an alkenyl-oxy group, a mono- or di-(alkenyl)-amino group, an alkenyl-carbonyl group, an alkenyl-oxy-carbonyl group, , mono- or di-(alkenyl)-amino-carbonyl, alkenyl-carbonyl-oxy, mono- or di-(alkenyl-carbonyl)-amino, aryl-oxy, mono- or di-(aryl)-amino, aryl-carbonyl, aryl-oxy-carbonyl, mono- or di-(aryl)-amino-carbonyl, aryl-carbonyl-oxy, mono- or di-(aryl-carbonyl)-amino, aryl-oxy, aryl-carbonyl, aryl-oxy-carbonyl, aryl-carbonyl-oxy, etc., or a combination thereof. The number of substituents is preferably 1 to 3.

In formula (1), the "monovalent alkyl group optionally substituted with one or more hydroxyl groups" includes, for example, an alkyl group having one or more hydroxyl groups, an alkenyl group having one or more hydroxyl groups, an aryl group having one or more hydroxyl groups, an alkyl group substituted with an aryl group having one or more hydroxyl groups, an alkenyl group substituted with an aryl group having one or more hydroxyl groups, an aryl group substituted with an alkyl group having one or more hydroxyl groups, an aryl group substituted with an alkenyl group having one or more hydroxyl groups, an aryl group substituted with an aryl group having one or more hydroxyl groups, and the like, preferably an alkyl group having one or more hydroxyl groups, or an alkyl group substituted with an aryl group having one or more hydroxyl groups. The number of hydroxyl groups in the "monovalent alkyl group optionally substituted with one or more hydroxyl groups" is preferably 1 to 3, and particularly preferably 1. The "optionally substituted monovalent alkyl group having one or more hydroxyl groups" is preferably bonded to different silicon atoms. In one embodiment, a phenolic hydroxyl group having a hydroxyl group on an aromatic group is preferred. That is, in one embodiment, the hydroxyl-containing siloxane compound (A-1) is preferably a phenolic hydroxyl-containing siloxane compound from the viewpoint of reactivity with the epoxy resin (C).

The "optionally substituted monovalent alkyl group" in formula (1) includes, for example, alkyl, alkenyl, aryl, aryl-substituted alkyl, aryl-substituted alkenyl, alkyl-substituted aryl, alkenyl-substituted aryl, aryl-substituted aryl, etc., preferably alkyl, particularly preferably methyl.

In formula (1), a chain siloxane is preferred, that is, at least two of the 2n+2 ^R1s and the 2 ^R2s are independently monovalent alkyl groups optionally substituted with one or more hydroxyl groups, and the other are independently monovalent alkyl groups optionally substituted, and a cyclic siloxane skeleton is not formed. It is also preferred that at least two of the 2n+2 ^R1s and the 2 ^R2s are independently monovalent alkyl groups having one or more hydroxyl groups, and the other are independently monovalent alkyl groups. It is even more preferred that at least two of the 2n+2 ^R1s and the 2 ^R2s are independently alkyl groups having one or more hydroxyl groups, or alkyl groups substituted with aryl groups having one or more hydroxyl groups, and the other are independently alkyl groups.

In formula (1), n represents an integer greater than 1, preferably an integer between 2 and 2,000, more preferably an integer between 2 and 1,000, and even more preferably an integer between 5 and 500.

Examples of commercially available products of the hydroxyl group-containing siloxane compound (A-1) include "X-22-160AS", "KF-6001", "KF-6002", "KF-6003", "X-22-4039", and "X-22-4015" (carbinol hydroxyl group-containing siloxane compounds) manufactured by Shin-Etsu Chemical Co., Ltd., and "KF-2201" and "X-22-1821" (phenolic hydroxyl group-containing siloxane compounds) manufactured by Shin-Etsu Chemical Co., Ltd.

(A-1) The weight average molecular weight (Mw) of the hydroxyl group-containing siloxane compound may preferably be 50,000 or less, more preferably 20,000 or less. The lower limit of the weight average molecular weight (Mw) may preferably be 500 or more, more preferably 1,000 or more. (A-1) The number average molecular weight (Mn) of the hydroxyl group-containing siloxane compound may preferably be 50,000 or less, more preferably 20,000 or less. The lower limit of the number average molecular weight (Mn) may preferably be 500 or more, more preferably 1,000 or more. The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC) (polystyrene conversion).

(A-1) The hydroxyl value of the hydroxyl-containing siloxane compound is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, still more preferably 100 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less. The lower limit of the hydroxyl value is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 25 mgKOH/g or more, and particularly preferably 30 mgKOH/g or more. The hydroxyl value is the amount of potassium hydroxide required to neutralize free acetic acid when the hydroxyl group of the compound is acetylated with acetic anhydride (in mg per 1 g of the compound).

The hydroxyl equivalent of the hydroxyl-containing siloxane compound (A-1) is preferably 10,000 g/eq. or less, more preferably 5,000 g/eq. or less, more preferably 3,000 g/eq. or less, and particularly preferably 2,000 g/eq. or less. The lower limit of the hydroxyl equivalent is preferably 100 g/eq. or more, more preferably 200 g/eq. or more, more preferably 500 g/eq. or more, and particularly preferably 700 g/eq. or more. The hydroxyl equivalent is the mass (g) of the compound per 1 equivalent of the hydroxyl group.

The viscosity (25°C) of the hydroxyl group-containing siloxane compound (A-1) is preferably 1,000 mm ² ·s or less, more preferably 500 mm ² ·s or less, more preferably 200 mm ² ·s or less, and particularly preferably 100 mm ² ·s or less. The lower limit of the viscosity (25°C) is preferably 10 mm ² ·s or more, more preferably 30 mm ² ·s or more, more preferably 50 mm ² ·s or more, and particularly preferably 60 mm ² ·s or more.

When the non-volatile components other than the (B) inorganic filler in the resin composition are set to 100% by mass, the content of the (A-1) hydroxyl-containing siloxane compound in the resin composition is 0.5% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, more preferably 1.8% by mass or more, and particularly preferably 2% by mass or more. When the non-volatile components other than the (B) inorganic filler in the resin composition are set to 100% by mass, the upper limit of the content of the (A-1) hydroxyl-containing siloxane compound in the resin composition is less than 5% by mass, preferably less than 4.5% by mass.

<Optional hardener other than component (A-1)> The resin composition of the present invention may further contain an optional hardener other than component (A-1).

The optional hardener other than the component (A-1) is a hardener that does not have both a hydroxyl group and a siloxane bond, for example, a compound that has atoms selected from hydrogen atoms, carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms as constituent atoms and that can harden the epoxy resin (C). The optional hardener other than the component (A-1) is not particularly limited, but examples thereof include phenolic hardeners, naphthol hardeners, acid anhydride hardeners, amine hardeners, active ester hardeners, benzoxazine hardeners, cyanate hardeners, and carbodiimide hardeners. The optional hardener other than the component (A-1) may be used alone or in combination of two or more. The optional hardener other than the component (A-1) is preferably a hardener selected from a phenol hardener, a naphthol hardener, an amine hardener, an active ester hardener, and an acid anhydride hardener, and particularly preferably an acid anhydride hardener.

As the phenolic hardener and the naphthol hardener, from the viewpoint of heat resistance and water resistance, a phenolic hardener having a novolac structure or a naphthol hardener having a novolac structure is preferred. From the viewpoint of adhesion to the object, a nitrogen-containing phenolic hardener or a nitrogen-containing naphthol hardener is preferred, and a phenolic hardener containing a triazine skeleton or a naphthol hardener containing a triazine skeleton is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, a phenolic novolac resin containing a triazine skeleton is preferred. Specific examples of phenol-based hardeners and naphthol-based hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku, "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemical & Material, and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "TD-2090-60M" manufactured by DIC Corporation.

Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule, and preferably those having two or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and diisocyanate. benzenetetracarboxylic 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(anhydrotrimellitate), styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid, and the like. Commercially available products of anhydride-based hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Chemical Co., Ltd., "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd., and "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

Examples of the amine-based curing agent include those having one or more (preferably two 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 curing agent is preferably a primary amine or a diamine, 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-phenylenediamine, m-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino -4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Amine hardeners that can be used are commercially available products, such as "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 Co., Ltd.

The active ester curing agent is not particularly limited, but generally, it is preferred to use a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, o-cresol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-phentriol (phloroglucin), benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

Specifically, preferred are active ester compounds containing a dicyclopentadiene diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolacs, and active ester compounds containing benzoylated products of phenol novolacs. Among them, preferred are active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene diphenol structure. The so-called "dicyclopentadiene diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

As for commercially available active ester curing agents, as active ester compounds containing a dicyclopentadiene-type diphenol structure, there can be cited "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", " Examples of the active ester compounds containing a naphthalene structure include "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", and "EXB-8150L-65T" (manufactured by DIC Corporation); examples of active ester curing agents of acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds of benzoylated phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industries, Ltd.

Examples of the cyanate curing agent include those derived from bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylpropane) Difunctional cyanate resins such as bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins such as phenol novolac and cresol novolac, and prepolymers of these cyanate resins partially triazinated. Specific examples of cyanate curing agents include "PT30" and "PT60" manufactured by Lonza Japan (both are phenol novolac type polyfunctional cyanate resins), "BA230", "BA230S75" (prepolymers of trimers obtained by triazinizing part or all of bisphenol A dicyanate), and the like.

Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

The reactive group equivalent of any curing agent other than the component (A-1) is preferably 50 g/eq. to 3,000 g/eq., more preferably 100 g/eq. to 1,000 g/eq., more preferably 100 g/eq. to 500 g/eq., and particularly preferably 100 g/eq. to 300 g/eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of the reactive group. The reactive group is, for example, an aromatic hydroxyl group in the case of a phenolic curing agent or a naphthol curing agent, an active ester group in the case of an active ester curing agent, and an acid anhydride group in the case of an acid anhydride curing agent, and varies depending on the type of the curing agent.

The content of any curing agent other than the component (A-1) in the resin composition is not particularly limited, but when the non-volatile components other than the (B) inorganic filler in the resin composition are taken as 100 mass%, it is, for example, 99.5 mass% or less, 95 mass% or less, 90 mass% or less, 80 mass% or less, preferably 70 mass% or less, 60 mass% or less, further preferably 50 mass% or less, 45 mass% or less, more preferably 40 mass% or less, 38 mass% or less, and particularly preferably 36 mass% or less. The lower limit of the content of any curing agent other than the component (A-1) in the resin composition is not particularly limited, and when the non-volatile components other than the (B) inorganic filler in the resin composition are taken as 100 mass %, it may be, for example, 0 mass % or more, 5 mass % or more, 10 mass % or more, 15 mass % or more, 20 mass % or more, 25 mass % or more, 30 mass % or more, 32 mass % or more, 34 mass % or more, etc.

When the (A) curing agent contains any curing agent other than the (A-1) component, the content of the (A-1) hydroxyl-containing siloxane compound in the resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, based on 100% by mass of the total amount of the (A) curing agent. The upper limit of the content of the (A-1) hydroxyl-containing siloxane compound in the resin composition is not particularly limited, but is preferably 80% by mass or less, more preferably 50% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, based on 100% by mass of the total amount of the (A) curing agent.

<(B) Inorganic filler> The resin composition of the present invention further contains (B) an inorganic filler.

(B) The material of the inorganic filler is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, aluminite, 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. Silicon dioxide and aluminum oxide are particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Preferably, the silica is spherical silica. (B) The inorganic filler may be used alone or in combination of two or more.

Commercially available products of (B) inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs; "UFP-30" manufactured by Denka; "Shirufiru NSS-3N", "Shirufiru NSS-4N", and "Shirufiru NSS-5N" manufactured by Tokuyama Co., Ltd.; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs; and "DAW-03" and "FB-105FD" manufactured by Denka Co., Ltd.

(B) The average particle size of the inorganic filler is not particularly limited, but is preferably 40 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, more preferably 0.5 μm or more, more preferably 1 μm or more, more preferably 3 μm or more, and particularly preferably 5 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction-scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared based on the volume by 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 obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them by ultrasound for 10 minutes. For the measurement sample, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source is set to blue and red. The volume-based particle size distribution of the inorganic filler is measured by a flow cell method, and the average particle size as the median particle size is calculated from the obtained particle size distribution. Examples of laser diffraction particle size distribution measuring devices include "LA-960" manufactured by Horiba, Ltd.

(B) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.01 m ² /g or more, more preferably 0.1 m ² /g or more, and particularly preferably 0.2 m ² /g or more. The upper limit is not particularly limited, but is preferably 50 m ² /g or less, more preferably 20 m ² /g or less, 10 m ² /g or less, or 5 m ² /g or less. The specific surface area of the inorganic filler 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 multipoint method.

From the viewpoint of improving moisture resistance and dispersibility, the (B) inorganic filler is preferably treated with one or more surface treatment agents selected from the group consisting of aminosilane coupling agents, epoxysilane coupling agents, butylsilane coupling agents, alkoxysilane compounds, organic silazane compounds, and titanate coupling agents. Commercially available products of surface treatment agents include, for example, "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM803" (3-hydroxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., and "SZ-3 1" (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), Shin-Etsu Chemical Co., Ltd. "KBM503" (3-methacryloyloxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM5783", etc.

The degree of surface treatment by the surface treatment agent is preferably set within a specified range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% by mass to 5% by mass of the surface treatment agent, more preferably 0.2% by mass to 3% by mass, and even more preferably 0.3% by mass to 2% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated based on the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ ^m2 or more, more preferably 0.1 mg/ ^m2 or more, and more preferably 0.2 mg/ ^m2 or more. On the other hand, from the perspective of preventing the increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is preferably 1.0 mg/ ^m2 or less, more preferably 0.8 mg/m2 or ^less , and more preferably 0.5 mg/ ^m2 or less.

(B) The amount of carbon per unit surface area of the 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 can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

When all non-volatile components in the resin composition are set to 100% by mass, the content of the (B) inorganic filler in the resin composition is 60% by mass or more, preferably 65% by mass or more, more preferably 70% by mass or more, 75% by mass or more, more preferably 78% by mass or more, 80% by mass or more, and particularly preferably 82% by mass or more, 83% by mass or more. The upper limit of the content of the (B) inorganic filler in the resin composition is not particularly limited, and when all non-volatile components in the resin composition are set to 100% by mass, it can be, for example, 98% by mass or less, 95% by mass or less, 90% by mass or less, etc.

The content mass ratio of the (B) inorganic filler to the (A-1) hydroxyl group-containing siloxane compound in the resin composition ((B) component/(A-1) component) is not particularly limited, but is preferably 20 or more, more preferably 50 or more, more preferably 80 or more, and particularly preferably 100 or more. The upper limit of the content mass ratio ((B) component/(A-1) component) is not particularly limited, but is preferably 2,000 or less, more preferably 1,000 or less, more preferably 500 or less, and particularly preferably 350 or less.

<(C) Epoxy resin> The resin composition of the present invention may further include (C) epoxy resin as an optional component. The so-called (C) epoxy resin means a resin having an epoxy group. (C) Epoxy resin is a component that can be cured by (A) curing agent.

Examples of the epoxy resin (C) 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, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butyl-catechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, and the like. Resins, glycyrrhizin type epoxy resins, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins The epoxy resins may be cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, naphthyl ether type epoxy resins, trihydroxymethyl type epoxy resins, tetraphenylethane type epoxy resins, isocyanurate type epoxy resins, phenol benzyl formamide type epoxy resins, phenol peptide type epoxy resins, etc. (C) The epoxy resins may be used alone or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin (C). The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile component of the epoxy resin (C) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The epoxy resin includes an epoxy resin that is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). The epoxy resin in the resin composition of the present invention may include only a liquid epoxy resin, or may include only a solid epoxy resin, or may include a combination of a liquid epoxy resin and a solid epoxy resin. The epoxy resin in the resin composition of the present invention is preferably a combination of a liquid epoxy resin and a solid epoxy resin.

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

As the liquid epoxy resin, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glycyrrhizin type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, dicyclopentadiene type epoxy resin, cyclohexanedimethanol type epoxy resin and epoxy resin having a butadiene structure.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Chemical Co., Ltd.; "ED-523T" (licorice alcohol type epoxy resin) manufactured by ADEKA; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagasechemtex Co., Ltd.; "Celloxide "2021P" manufactured by Daicel (epoxy resin with ester structure); "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" manufactured by Nippon Soda (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical & Material (liquid 1,4-glycidyl cyclohexane type epoxy resin), etc. These can 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.

As the solid epoxy resin, preferred are xylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, Resins, biphenyl type epoxy resins, naphthyl ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, phenol benzyl formamide type epoxy resins, phenol peptide 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", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-based epoxy resin) manufactured by DIC Corporation; "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 novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthalene type epoxy resin) manufactured by Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX7700" manufactured by Osaka Chemicals (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" manufactured by Mitsubishi Chemical (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical (bisphenol A type epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical (tetraphenylethane type epoxy resin); "WHR991S" manufactured by Nippon Kayaku Co., Ltd. (phenol benzyl formamide 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 as component (C) in combination, the mass ratio of the solid epoxy resin to the liquid epoxy resin (solid epoxy resin/liquid epoxy resin) is not particularly limited, but is preferably 0.2 or more, more preferably 0.5 or more, more preferably 1 or more, more preferably 1.3 or more, and particularly preferably 1.5 or more. The upper limit of the mass ratio of the solid epoxy resin to the liquid epoxy resin (solid epoxy resin/liquid epoxy resin) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, more preferably 3 or less, more preferably 2 or less, and particularly preferably 1.8 or less.

(C) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. to 5,000 g/eq., more preferably 60 g/eq. to 2,000 g/eq., more preferably 70 g/eq. to 1,000 g/eq., and even more preferably 80 g/eq. to 500 g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

(C) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and more preferably 400 to 1,500. The weight average molecular weight of the resin can be obtained as a polystyrene-equivalent value by measuring by gel permeation chromatography (GPC).

When the resin composition of the present invention includes (C) epoxy resin, the amount ratio of (C) epoxy resin to (A) hardener is preferably 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and even more preferably 1:0.4 to 1:1.4, measured as the ratio of [the number of epoxy groups in (C) epoxy resin]:[the number of reactive groups in (A) hardener (the total number of hydroxyl groups in (A-1) hydroxyl-containing siloxane compound and the number of reactive groups in hardeners other than (A-1))].

The content of the epoxy resin (C) in the resin composition is not particularly limited. When the non-volatile components other than the inorganic filler (B) in the resin composition are set to 100 mass%, it is preferably 90 mass% or less, 85 mass% or less, more preferably 80 mass% or less, 75 mass% or less, more preferably 70 mass% or less, 67 mass% or less, and particularly preferably 65 mass% or less, 63 mass% or less. The lower limit of the content of the epoxy resin (C) in the resin composition is not particularly limited. When the non-volatile components other than the inorganic filler (B) in the resin composition are set to 100 mass%, it can be, for example, 0 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, preferably 40 mass% or more, more preferably 50 mass% or more, more preferably 55 mass% or more, and particularly preferably 60 mass% or more.

<(D) Hardening accelerator> The resin composition of the present invention may further contain (D) a hardening accelerator as an optional component. (D) The hardening accelerator has the function of hardening (C) the epoxy resin.

(D) The hardening accelerator is not particularly limited, but examples thereof include phosphorus-based hardening accelerators, urea-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 and imidazole-based hardening accelerators are particularly preferred. The hardening accelerators may be used alone or in combination of two or more.

Phosphorus-based hardening accelerators include, for example, aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid, tetrabutylphosphonium hydrohexahydrophthalate, tetrabutylphosphonium cresol novolac trimer salt, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, Aromatic phosphonium salts such as p-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methylphenyl)phosphine, aliphatic phosphines such as tricyclohexyl phosphine, dibutylphenyl phosphine, di-tert-butylphenyl phosphine, methyldiphenyl phosphine, ethyldiphenyl phosphine, butyldiphenyl phosphine, diphenylcyclohexyl phosphine, triphenylphosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( The invention also includes aromatic phosphines such as tris(2,3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

Examples of the urea-based hardening accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1 -dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] and the like.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine is 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, cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 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-phenylimidazole Imidazole compounds such as isocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazolium, 2-phenylimidazolium, and adducts of imidazole compounds with epoxy resins.

As the imidazole-based hardening accelerator, a commercially available product can be used, and an example thereof is "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

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

The content of the (D) curing accelerator in the resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, based on 100% by mass of the non-volatile components other than the (B) inorganic filler in the resin composition. The lower limit of the content of the (D) curing accelerator in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.0001% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, etc., based on 100% by mass of the non-volatile components other than the (B) inorganic filler in the resin composition.

<(E) Other additives> The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include organic fillers such as rubber particles, polyamide microparticles, and polysilicone particles; thermoplastic resins such as polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfide resins, polyethersulfide resins, polyphenylene ether resins, polyetheretherketone resins, and polyester resins; organic copper compounds, organic zinc compounds, and organic cobalt compounds; Organic metal compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc.; polymerization inhibitors such as hydroquinone, o-catechol, o-pyroquinone, phenothiazine, etc.; leveling agents such as polysilicone leveling agents and acryl polymer leveling agents; tackifiers such as bentonite and montmorillonite; polysilicone defoaming agents and acryl defoaming agents Defoaming agents such as fluorocarbon defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; UV absorbers such as benzotriazole UV absorbers; adhesion enhancers such as urea silane; adhesion enhancers such as triazole adhesion enhancers, tetrazole adhesion enhancers, and triazine adhesion enhancers; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; stilbene (stilbene) ne) derivatives, etc.; fluorine-based surfactants, silicone-based surfactants, etc.; phosphorus-based flame retardants (e.g., phosphate compounds, phosphazene compounds, hypophosphorous acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g., antimony trioxide), etc. The additives may be used alone or in combination of two or more in any ratio. (E) The content of other additives may be appropriately set by those having ordinary knowledge in the field of the present invention.

<(F) Organic solvent> The resin composition of the present invention may contain any organic solvent as a volatile component in addition to the non-volatile component mentioned above. As the (F) organic solvent, a well-known one can be appropriately used, and the type is not particularly limited. Examples of the (F) organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methoxypropionic acid methyl ester; ester-based solvents such as methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, etc.; ester-alcohol-based solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol), etc.; amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; sulfoxide-based solvents such as dimethyl sulfoxide; nitrile-based solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, methylcyclohexane, etc.; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. (F) The organic solvent may be used alone or in combination of two or more in any ratio. In one embodiment, the amount of (F) the organic solvent is preferably as small as possible (for example, 0.5 mass % or less, 0.1 mass % or less, 0.01 mass % or less when the non-volatile component in the resin composition is 100 mass %), and is particularly preferably not contained.

<Manufacturing method of resin composition> The resin composition of the present invention can be manufactured by, for example, the following method: (A) a hardener, (B) an inorganic filler, (C) an epoxy resin as required, (D) a hardening accelerator as required, (E) other additives as required, and (F) an organic solvent as required are added to any reaction container in any order and/or partially or all at the same time, and mixed to obtain a resin composition. In addition, during the process of adding and mixing the components, the temperature can be appropriately set, and heating and/or cooling can be performed temporarily or throughout the process. In addition, during the process of adding and mixing the components, stirring or shaking can be performed. When or after adding and mixing the components, the resin composition may be stirred using a stirring device such as a mixer to be uniformly dispersed.

<Characteristics of resin composition> The resin composition of the present invention is a resin composition comprising (A) a curing agent and (B) an inorganic filler, and the component (A) comprises the hydroxyl-containing siloxane compound (A-1), and the content of the component (A-1) is less than 5% by mass when the non-volatile components other than the component (B) in the resin composition are taken as 100% by mass, and the content of the component (B) is 60% by mass or more when the total non-volatile components in the resin composition are taken as 100% by mass. Therefore, the generation of flow marks and warping after molding can be suppressed, and a cured product having excellent heat-peel tape adhesion can be obtained.

In one embodiment, since the cured product of the resin composition of the present invention can suppress warping, a sample substrate including a silicon wafer and a cured product layer of the resin composition is prepared as in the following Test Example 1. When the warping amount of the sample substrate is measured at 25° C. in accordance with JEITA EDX-7311-24, the warping amount can be less than 3 mm.

In one embodiment, since the cured product of the resin composition of the present invention has excellent adhesion to the heat-release tape, for example, when a sample substrate comprising a silicon wafer and a resin composition is prepared as in the following Experimental Example 2, even if the sample substrate is placed at 23°C for 30 minutes, no peeling occurs between the heat-release tape and the resin composition.

In one embodiment, since the cured product of the resin composition of the present invention can suppress the generation of flow marks after molding, when a sample is prepared as in the following Test Example 3 and the appearance of the resin composition layer is observed, the area occupied by the flow marks in the entire surface of the resin composition layer can be less than 20%.

<Application of resin composition> The resin composition of the present invention may contain (C) epoxy resin, or may be used by mixing with (C) epoxy resin before use. Hereinafter, the resin composition of the present invention containing (C) epoxy resin, or the resin composition obtained by mixing (C) epoxy resin into the resin composition of the present invention, is referred to as "epoxy resin composition". Therefore, the resin composition of the present invention can be used directly, or can be used in the same application as the epoxy resin composition described below by mixing with (C) epoxy resin.

The cured epoxy resin composition of the present invention is particularly useful for the sealing layer and insulating layer of a semiconductor due to the above advantages. Therefore, the epoxy resin composition of the present invention can be used as a resin composition for semiconductor sealing or insulating layer.

For example, the epoxy resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for insulating layer of a 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).

Furthermore, for example, the epoxy resin composition of the present invention can be suitably used as a resin composition for sealing a semiconductor chip in a semiconductor chip package (resin composition for semiconductor chip sealing).

Semiconductor chip packages to which the sealing layer or insulating layer formed by the cured epoxy resin composition of the present invention can be applied include, for example, FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out WLP (Wafer Level Package), Fan-in WLP, Fan-out PLP (Panel Level Package), and Fan-in PLP.

Furthermore, the epoxy resin composition of the present invention can be used as an underfill material, and can also be used as a MUF (Molding Under Filling) material used after connecting a semiconductor chip to a substrate.

Furthermore, the epoxy resin composition of the present invention can be used in a wide range of resin compositions such as resin sheets, prepregs and other sheet-like laminate materials, liquid materials such as resin inks for solder resists, etc., grain bonding materials, hole filling resins, and component embedding resins.

<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 comprising the resin composition of the present invention as an epoxy resin composition. That is, when forming the resin composition layer, the resin composition of the present invention containing (C) epoxy resin is used, or a resin composition obtained by mixing (C) epoxy resin into the resin composition of the present invention is used.

The thickness of the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less, from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 100 μm or more.

The thickness of the cured product obtained by curing the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the cured product is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 100 μm or more.

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

When a film made of a plastic material is used as the support, the plastic material may include polyesters such as polyethylene terephthalate (hereinafter referred to as "PET") and polyethylene naphthalate (hereinafter referred to as "PEN"), polycarbonate (hereinafter referred to as "PC"), acrylic polymers such as polymethyl methacrylate (hereinafter referred to as "PMMA"), cyclic polyolefin, triacetyl cellulose (hereinafter referred to as "TAC"), polyether sulfide (hereinafter 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 the 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 a single metal containing copper or a foil made of an alloy containing copper and other metals (such as 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 polishing, corona treatment, anti-static treatment, and the like.

In addition, as the support body, a support body with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used for the release layer of the support body with a release layer, for example, at least one release agent selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins can be cited. As commercially available products of the release agent, for example, alkyd resin-based release agents such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation can be cited. Examples of the support body with a release layer include "Lumirror T60" manufactured by Toray Industries, Inc., "PUREX" manufactured by Teijin Ltd., and "Unipeel" manufactured by Unitika Co., Ltd.

The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

A resin sheet can be produced by coating an epoxy resin composition, for example, on a support using a coating device such as a die coater. Alternatively, a resin varnish can be prepared by dissolving the epoxy resin composition in an organic solvent as required, and the resin varnish can be coated to produce a resin sheet. Coating properties can be improved by adjusting the viscosity using a solvent. When an epoxy resin composition or a resin varnish containing an organic solvent is used, the epoxy resin composition or the resin varnish is usually dried after coating to form a resin composition layer.

Drying can be carried out by known methods such as heating and hot air blowing. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. It varies depending on the boiling point of the organic solvent in the epoxy resin composition or resin varnish. For example, if an epoxy resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition layer can be formed by drying it at 50°C to 150°C for 3 minutes to 10 minutes.

As required, the resin sheet may include any layer other than the support and the resin component layer. For example, in the resin sheet, the surface that is not bonded to the support of the resin component layer (i.e., the surface on the opposite side of the support) may be provided with a protective film in conjunction with the support. The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent impurities from adhering to or scratching the surface of the resin component layer. If the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, the resin sheet can be stored by being rolled into a tube.

When manufacturing semiconductor chip packages, resin sheets can be used to form insulation layers (resin sheets for insulation of semiconductor chip packages). For example, resin sheets can be used to form insulation layers of circuit boards (resin sheets for insulation layers of circuit boards). 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 a semiconductor chip (resin sheet for semiconductor chip sealing). Examples of semiconductor chip packages that can be used include Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, and Fan-in type PLP.

In addition, the resin sheet can also be used as a MUF material 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 suitably used to form an insulation layer of a circuit board such as a printed wiring board.

<Circuit board> The circuit board of the present invention includes an insulating layer formed by a cured product of an epoxy resin composition obtained from the resin composition of the present invention. The circuit board can be manufactured by a manufacturing method including, for example, the following steps (1) and (2). (1) A step of forming a resin composition layer of an epoxy resin composition on a substrate using the resin composition of the present invention. (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-rolled steel (SPCC) substrates, etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Furthermore, the substrate may have a metal layer such as copper foil on the surface as a part of the substrate. For example, a substrate having a first metal layer and a second metal layer that can be peeled off on both surfaces may be used. When such a substrate is used, a conductive layer serving as a wiring layer is usually formed on the surface of the second metal layer that is opposite to the first metal layer, and the wiring layer can function as a circuit wiring. As a substrate having such a metal layer, for example, there is 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 one or both surfaces of the substrate. In the following description, the substrate and the conductive layer formed on the surface of the substrate will be appropriately referred to as a "substrate with a wiring layer". As the conductive material contained in the conductive layer, there can be cited a material containing one or more metals selected from the group consisting of, for example, gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. As the conductive material, a single metal or an alloy can be used. As the alloy, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy and a copper-titanium alloy) can be cited. Among them, from the viewpoint of versatility, cost, and ease of patterning of the conductor layer formation, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal, and 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; copper as a single metal is particularly preferred.

In order to make the conductor layer function as a wiring layer, for example, the conductor layer can be patterned. At this time, the line width (circuit width)/spacing (width between circuits) ratio of the conductor layer is not particularly limited, and is preferably 20/20μm or less (i.e., the spacing is 40μm or less), more preferably 10/10μm or less, more preferably 5/5μm or less, more preferably 1/1μm or less, and particularly preferably 0.5/0.5μm or more. The overall spacing of the conductor layer does not need to be the same. The minimum spacing of the conductor layer can be set to, for example, 40μm or less, 36μm or less, or 30μm or less.

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

The conductive layer can be formed by a method including, for example, 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 specified conditions using a photomask to form a pattern to obtain a patterned dry film; a step of using the developed patterned dry film as a plating mask and forming a conductive layer by a plating method such as an electrolytic plating method; and a step of peeling off the patterned dry film. As the dry film, a photosensitive dry film containing a photoresist composition can be used, and a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. 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 stripping of the dry film can be carried out using an alkaline stripping solution such as a sodium hydroxide solution.

After the substrate is prepared, a resin composition layer is formed on the substrate. If a conductor layer is formed on the surface of the substrate, the resin composition layer is preferably formed such that the conductor layer is buried in the resin composition layer.

The formation of the resin composition layer can be performed by laminating a resin sheet and a substrate, for example. The lamination can be performed by, for example, heating and pressing the resin sheet onto the substrate from the side of the support so that the resin composition layer is attached to the substrate. As a member for heating and pressing the resin sheet onto the substrate (hereinafter sometimes referred to as a "heating and pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller, etc.) can be cited. However, it is preferred that the heating and pressing member is not directly pressed onto the resin sheet, but the resin sheet is pressed through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface irregularities of the substrate.

The lamination of the substrate and the resin sheet can 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. The 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 pressing the heat-pressing member from the support body side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be set to the same conditions as the heat-pressing conditions for the lamination. In addition, the lamination and smoothing treatment can be performed continuously using a vacuum laminating machine.

The resin composition layer can be formed by, for example, compression molding. The molding conditions can be the same as those of the resin composition layer forming method in the step of forming the sealing layer of the semiconductor chip package described later.

After forming the resin composition layer on the substrate, the resin composition layer is heat-cured to form an insulating layer. Although the heat-curing conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is generally in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, 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-cured, the resin composition layer may be pre-heated at a temperature lower than the curing temperature. For example, before the resin composition layer is heat-cured, the resin composition layer may be pre-heated at a temperature of 50°C to 120°C (preferably 60°C to 110°C, and more preferably 70°C to 100°C) for 5 minutes or more (preferably 5 minutes to 150 minutes, and more preferably 15 minutes to 120 minutes).

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

The manufacturing method of the circuit board may include, for example, the following step: after forming the insulating layer, the surface of the insulating layer is polished. The polishing method is not particularly limited. The surface of the insulating layer can be polished using, for example, a surface grinding disc.

The manufacturing method of the circuit substrate may include, for example, a step (3) of connecting the conductor layers between layers, for example, a step of opening holes on the insulating layer. In this way, holes such as through holes and through holes can be formed on the insulating layer. Examples of methods for forming through holes include laser irradiation, etching, mechanical drilling, etc. The size or shape of the through hole can be appropriately determined according to the design of the circuit substrate. In addition, step (3) can be performed by grinding or grinding the insulating layer to connect the layers between layers.

After the through hole is formed, it is preferred to perform a step of removing the glue residue in the through hole. This step is called a desmearing step. For example, when the conductive layer is formed on the insulating layer by a plating step, a wet desmearing treatment can be performed on the through hole. Also, when the conductive layer is formed on the insulating layer by a sputtering step, a dry desmearing step such as a plasma treatment step can be performed. Furthermore, the insulating layer can also be roughened by the desmearing 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 hole is usually roughened. The roughening treatment may be either a dry roughening treatment or a wet roughening treatment. Examples of dry roughening treatments include plasma treatment and the like. Furthermore, examples of wet roughening treatments include a method of sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.

After forming the through-holes, a conductive layer can be formed on the insulating layer. By forming the conductive layer at the position where the through-holes are formed, the newly formed conductive layer can be electrically connected to the conductive layer on the surface of the substrate to achieve inter-layer connection. The conductive layer can be formed by, for example, plating, sputtering, evaporation, etc., among which plating is preferred. In a suitable embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method and a full-additive method to form a conductive layer having a desired wiring pattern. Furthermore, if 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 formed conductive layer may 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 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 in a manner corresponding to the desired wiring pattern to expose a portion of the coating seed layer. An electrolytic coating layer is formed on the exposed coating seed layer by electrolytic plating, and the mask pattern is removed. Thereafter, the unnecessary coating seed layer is removed by etching or the like, so that a conductive layer having the desired wiring pattern can be formed. In addition, when forming the conductive layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

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

<Semiconductor chip package> The semiconductor chip package related to 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 may be any conditions that allow the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board to be conductively connected. For example, the conditions used in flip chip mounting of the semiconductor chip may be used. Alternatively, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

As an example of a bonding method, there can be cited 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 in the range of 130°C to 200°C, and more preferably in the range of 140°C to 180°C), and the pressing time is usually in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

As another example of the bonding method, there is a method of bonding a semiconductor chip to a circuit board by reflowing. 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 can be filled with a molded bottom filler. As the molded bottom filler, the above-mentioned resin composition or the above-mentioned resin sheet can be used.

The semiconductor chip package according to the second embodiment of the present invention comprises a semiconductor chip and a hardened resin composition for sealing the semiconductor chip. In such a semiconductor chip package, the hardened resin composition generally functions as a sealing layer. The semiconductor chip package according to the second embodiment may be, for example, a Fan-out type WLP.

Such a method for manufacturing a semiconductor chip package includes the following steps: (A) laminating a temporary fixing film on a substrate; (B) temporarily fixing a semiconductor chip on the temporary fixing film; (C) forming a sealing layer on the semiconductor chip; (D) peeling the substrate and the temporary fixing film from the semiconductor chip; (E) forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film are peeled; (F) forming a redistribution layer as a conductive layer on the redistribution layer; and (G) forming a solder resist layer on the redistribution layer. Furthermore, the aforementioned method for manufacturing a semiconductor chip package may also include the step of (H) cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into individual pieces.

(Step (A)) Step (A) is a step of laminating a temporary fixing film on a substrate. The lamination conditions of the substrate and the temporary fixing film can be the same as the lamination conditions of the substrate and the resin sheet in the method for manufacturing a circuit board.

Examples of the substrate include silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheets (SPCC), substrates such as FR-4 substrates in which glass fibers are infiltrated with epoxy resins and then heat-cured, and substrates such as BT resins containing dimaleimide triazine resins.

The temporary fixing film may be any material that can be peeled off from the semiconductor chip and temporarily fix the semiconductor chip. Examples of commercially available products include "REVALPHA" manufactured by Nitto Denko Corporation.

(Step (B)) Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonding machine or a die bonder. The configuration layout and number of semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor chip package, etc. For example, the semiconductor chips can be arranged in a matrix of multiple rows and multiple columns for temporary fixing.

(Step (C)) Step (C) is a step of forming a sealing layer on a semiconductor chip. The sealing layer is formed by hardening the resin composition described above. Generally, the sealing layer is formed by a method comprising the steps of forming a resin composition layer on a semiconductor chip and thermally hardening the resin composition layer to form the sealing layer.

Preferably, the resin composition layer is formed by compression molding. Generally speaking, the compression molding method is to arrange the semiconductor chip and the resin composition in a mold, apply pressure and heat to the resin composition in the mold as needed, to form the resin composition layer covering the semiconductor chip.

The specific operation of the compression molding method can be as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. In addition, a resin composition is applied to the semiconductor chip that is temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition is fixed to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper mold and the lower mold are combined, and heat and pressure are applied to the resin composition to perform compression molding.

The specific operation of the compression molding method can also be performed in the following manner, for example. An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed in the lower mold. A semiconductor chip is fixed to the upper mold together with a substrate and a temporary fixing film. Thereafter, the upper mold and the lower mold are combined in such a manner that the resin composition placed in the lower mold is in contact with the semiconductor chip fixed in the upper mold, and heat and pressure are applied to perform compression molding.

The molding conditions vary depending on the composition of the resin composition, and appropriate conditions that can achieve good sealing can be adopted. For example, the temperature of the mold during molding is preferably 70°C or higher, more preferably 80°C or higher, particularly preferably 90°C or higher, preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. In addition, the pressure applied during molding is preferably 1MPa or higher, more preferably 3MPa or higher, particularly preferably 5MPa or higher, preferably 50MPa or lower, more preferably 30MPa or lower, and particularly preferably 20MPa or lower. The curing time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 3 minutes or longer, preferably 60 minutes or lower, more preferably 30 minutes or lower, and particularly preferably 20 minutes or lower. Generally speaking, the mold can be removed after the resin composition layer is formed. The mold can be removed before or after the resin composition layer is thermally hardened.

The formation of the resin composition layer can be performed by laminating the resin sheet and the semiconductor chip. For example, the resin composition layer of the resin sheet and the semiconductor chip can be formed on the semiconductor chip by heating and pressing the resin composition layer of the resin sheet and the semiconductor chip. The lamination of the resin sheet and the semiconductor chip can generally be performed in the same manner as the lamination of the resin sheet and the substrate in the manufacturing method of the circuit board, but using the semiconductor chip instead of the substrate.

After forming a resin composition layer on a semiconductor chip, the resin composition layer is heat-cured to obtain a sealing layer covering the semiconductor chip. Accordingly, the semiconductor chip can be sealed by the cured resin composition. The heat-curing conditions of the resin composition layer can be the same as the heat-curing conditions of the resin composition layer in the method for manufacturing a circuit board. Furthermore, before heat-curing the resin composition layer, a preliminary heat treatment can be performed by heating the resin composition layer at a temperature lower than the curing temperature. The treatment conditions of the preliminary heat treatment can be the same as the treatment conditions of the preliminary heat treatment in the method for manufacturing a circuit board.

(Step (D)) Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. The peeling method is preferably a method suitable for the material of the temporary fixing film. As a peeling method, there can be exemplified a method of peeling the temporary fixing film by heating, foaming or expanding the temporary fixing film. Also, as a peeling method, there can be exemplified a method of irradiating the temporary fixing film with ultraviolet light through the substrate to reduce the adhesion of the temporary fixing film and then peeling it.

In the method of peeling off the temporary fixing film by heating, foaming or expanding it, the heating condition is usually 100℃~250℃ for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of peeling off after irradiating ultraviolet rays to reduce the adhesive force of the temporary fixing film, the irradiation amount of ultraviolet rays is usually 10mJ/ ^cm2 ~1000mJ/ ^cm2 .

(Step (E)) Step (E) is a step of forming a redistribution layer as an insulating layer on the substrate of the semiconductor chip and the surface where the temporary fixing film is peeled off.

The material of the redistribution forming layer can be any material having insulation properties. Among them, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing the semiconductor chip package. In addition, as the thermosetting resin, the resin composition of the present invention can be used.

After the redistribution formation layer is formed, a through hole may be formed on the redistribution formation layer in order to connect the semiconductor chip to the redistribution formation layer.

If the material of the redistribution forming layer is a photosensitive resin, generally speaking, the method for forming the through hole is to irradiate the surface of the redistribution forming layer with active energy rays through a mask pattern to photoharden the irradiated portion of the redistribution forming layer. Examples of active energy rays include ultraviolet rays, visible rays, electron rays, X-rays, etc., with ultraviolet rays being particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. Examples of the exposure method include: a contact exposure method in which a mask pattern is adhered to the redistribution forming layer and then exposed; and a non-contact exposure method in which a mask pattern is not adhered to the redistribution forming layer and then exposed using parallel light.

After the redistribution formation layer is photocured, the redistribution formation layer is developed and the unexposed portion is removed to form a through hole. The development may be either wet development or dry development. As the development method, for example, there are immersion method, mixing method, spray method, brush coating method, scraping method, etc. From the perspective of analytical performance, the mixing method is suitable.

When the material of the redistribution forming layer is a thermosetting resin, the method of forming the through hole may be, for example, laser irradiation, etching, mechanical drilling, etc. Among them, laser irradiation is preferred. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide gas laser, a UV-YAG laser, or an excimer laser.

The shape of the through hole is not particularly limited, and is generally circular (slightly circular). The top port diameter of the through hole is preferably less than 50 μm, more preferably less than 30 μm, and more preferably less than 20 μm. Here, the so-called top port diameter of the through hole refers to the diameter of the opening of the through hole on the surface of the redistribution formation layer.

(Step (F)) Step (F) is a step of forming a redistribution layer as a conductive layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer can be the same as the method of forming a conductive layer on an insulating layer in the manufacturing method of a circuit board. Alternatively, steps (E) and (F) may be repeated to alternately stack the redistribution layer and the redistribution formation layer (build-up layer).

(Step (G)) Step (G) is a step of forming a solder resist layer on the redistribution layer. The material of the solder resist layer can be any material having insulation properties. Among them, photosensitive resins and thermosetting resins are preferred from the perspective of ease of manufacturing the semiconductor chip package. In addition, as the thermosetting resin, the resin composition of the present invention can be used.

In step (G), bump processing can be performed to form bumps as needed. The bump processing can be performed by using solder balls, solder plating, etc. In addition, the formation of through holes in the bump processing can be performed in the same way as in step (E).

(Step (H)) In addition to steps (A) to (G), the method for manufacturing a semiconductor chip package may include step (H). Step (H) is a step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into individual pieces. The method for cutting a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

<Semiconductor device> A semiconductor device is a semiconductor chip package. Examples of semiconductor devices 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) and transportation vehicles (such as motorcycles, cars, trains, ships, and airplanes). [Example]

The present invention is specifically described below by way of examples. The present invention is not limited to the examples. In addition, the "parts" used below to indicate quantity shall mean "parts by mass" unless otherwise specified.

<Example 1> A phenolic hydroxyl-containing siloxane compound ("KF-2201" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 38 mgKOH/g) 1 part, an acid anhydride curing agent ("HNA-100" manufactured by Shin-Nippon Chemical Co., Ltd., acid anhydride equivalent 179 g/eq.) 8 parts, silicon dioxide (average particle size 6.9 μm, specific surface area 3.4 m ² /g, surface treated with "KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd.) 120 parts, a bisphenol-type epoxy resin (Nippon Steel Chemical & A resin composition was prepared by uniformly dispersing 7 parts of "ZX1059" manufactured by Material Co., Ltd. (epoxy equivalent of about 165 g/eq., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), 5 parts of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 95 g/eq.), 2 parts of dicyclopentadiene type epoxy resin ("HP-7200L" manufactured by DIC Co., Ltd., epoxy equivalent of about 250 g/eq.), and 0.1 parts of imidazole type curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Industries, Ltd., 1-benzyl-2-phenylimidazole) using a stirrer to prepare a resin composition.

<Example 2> Except that the amount of the phenolic hydroxyl-containing siloxane compound ("KF-2201" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 38 mgKOH/g) used was changed from 1 part to 0.5 parts, the resin composition was obtained in the same manner as in Example 1.

<Example 3> A resin composition was obtained in the same manner as in Example 1 except that 165 parts of alumina (average particle size 6.0 μm, specific surface area 1.7 m ² /g, surface treated with "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 120 parts of silica (average particle size 6.9 μm, specific surface area 3.4 ^{m 2} /g, surface treated with "KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd.).

<Example 4> A resin composition was obtained in the same manner as in Example 2 except that 165 parts of alumina (average particle size 6.0 μm, specific surface area 1.7 m ² /g, surface treated with "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 120 parts of silica (average particle size 6.9 μm, specific surface area 3.4 ^{m 2} /g, surface treated with "KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd.).

<Example 5> Except that 0.5 parts of a siloxane compound containing a carboxyl type hydroxyl group ("KF-6002" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 35 mgKOH/g) was used instead of 1 part of a siloxane compound containing a phenolic hydroxyl group ("KF-2201" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 38 mgKOH/g), the resin composition was obtained in the same manner as in Example 1.

<Example 6> Except that 0.5 parts of a siloxane compound containing a carboxyl type hydroxyl group ("X-22-4039" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 58 mgKOH/g) was used instead of 1 part of a siloxane compound containing a phenolic hydroxyl group ("KF-2201" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 38 mgKOH/g), the resin composition was obtained in the same manner as in Example 1.

<Comparative Example 1> Except for changing the amount of the phenolic hydroxyl-containing siloxane compound ("KF-2201" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 38 mgKOH/g) used from 1 part to 3 parts, the resin composition was obtained in the same manner as in Example 1.

<Comparative Example 2> Except for not using a phenolic hydroxyl-containing siloxane compound ("KF-2201" manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value 38 mgKOH/g), the resin composition was obtained in the same manner as in Example 1.

<Test Example 1: Evaluation 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. Thereafter, the resin composition layer was thermally cured by heating at 180°C for 90 minutes. Thus, 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 ("Thermoire AXP" manufactured by Akorometrix). The measurement is performed in accordance with JEITA EDX-7311-24 stipulated by the Electronics and Information Technology Industries Association. Specifically, all data on the substrate surface in the measurement area is calculated by the least square method to obtain a hypothetical plane as a reference plane, and the difference between the minimum and maximum values in the vertical direction from the reference plane is obtained as the warp amount, and the following criteria are used for evaluation. "○": The warp amount is less than 3mm. "×": The warp amount is 3mm or more.

<Test Example 2: Evaluation of Adhesion of Thermal Release Tape> A thermal release tape ("REVALPHA No.3195V" manufactured by Nitto Denko Corporation) that is adhesive at room temperature but easily peelable when heated was attached to 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. Thus, a sample substrate including a silicon wafer and a resin composition was obtained. "○": After the sample substrate was placed at 23°C for 30 minutes, no peeling occurred between the heat peel tape and the resin composition. "×": After the sample substrate was placed at 23°C for 30 minutes, peeling occurred between the heat peel tape and the resin composition.

<Test Example 3: Evaluation of flow marks after molding> 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 as a sample. Afterwards, the appearance of the resin composition layer of the sample was observed and evaluated using the following criteria. "○": The area occupied by flow marks in the entire surface of the resin composition layer is less than 20%. "×": The area occupied by flow marks in the entire surface of the resin composition layer is more than 20%.

The non-volatile components of the resin compositions of Examples and Comparative Examples and their usage amounts, as well as the evaluation results of the test examples are shown in Table 1 below.

From the above results, it can be seen that when a resin composition containing (A-1) a hydroxyl group-containing siloxane compound and (B) an inorganic filler is used in a specified ratio, the generation of flow marks and warping after molding can be suppressed, and a cured product having excellent heat-peel tape adhesion can be obtained.

Claims (20)

A resin composition comprises (A) a curing agent, (B) an inorganic filler and (C) an epoxy resin, wherein the component (A) comprises (A-1) a hydroxyl-containing siloxane compound, and the component (A-1) comprises a siloxane compound represented by formula (1). wherein at least two of the 2n+2 R ^1s and the 2 R ^2s independently represent an optionally substituted monovalent alkyl group having one or more hydroxyl groups, and the others independently represent an optionally substituted monovalent alkyl group; or, at least two of the 2n+2 R ^1s independently represent an optionally substituted monovalent alkyl group having one or more hydroxyl groups, and the others independently represent an optionally substituted monovalent alkyl group, and the two R ^2s together show one -O- and are bonded to each other to form a cyclosiloxane skeleton, and n represents an integer greater than 2. When the non-volatile components other than the component (B) in the resin composition are taken as 100% by mass, the content of the component (A-1) is 0.5% by mass or more and less than 5% by mass. When all non-volatile components in the resin composition are taken as 100 mass %, the content of the component (B) is 60 mass % or more. The resin composition of claim 1, wherein the component (A-1) is a phenolic hydroxyl-containing siloxane compound. The resin composition of claim 1, wherein the component (A-1) has a chain siloxane skeleton. The resin composition of claim 1, wherein the hydroxyl value of the component (A-1) is 120 mgKOH/g or less. The resin composition of claim 1, wherein the component (A) further comprises a hardener selected from the group consisting of a phenol hardener, a naphthol hardener, an amine hardener, an active ester hardener, and an acid anhydride hardener. The resin composition of claim 1, wherein the content of the component (A-1) is 3% to 20% by mass, when the total amount of the component (A) is 100% by mass. The resin composition of claim 1, wherein component (B) is silicon dioxide. The resin composition of claim 1, wherein the content of the component (B) is 70% by mass or more, based on 100% by mass of all non-volatile components in the resin composition. The resin composition of claim 8, wherein the content of the component (B) is 80 mass % or more, when all non-volatile components in the resin composition are taken as 100 mass %. The resin composition of claim 1, wherein the mass ratio of component (B) to component (A-1) (component (B)/component (A-1)) is 50 to 1,000. The resin composition of claim 1 is used to form an insulating layer of a semiconductor chip package. The resin composition of claim 1 is used to form an insulating layer of a circuit substrate. The resin composition of claim 1 is used for sealing a semiconductor chip in a semiconductor chip package. A cured product obtained from the resin composition of any one of claims 1 to 13. A resin sheet comprises a support and a resin composition layer disposed on the support, wherein the resin composition layer comprises the resin composition of any one of claims 1 to 13. A circuit board includes an insulating layer formed by a cured product, wherein the cured product is a cured product obtained from the resin composition of any one of claims 1 to 13. A semiconductor chip package comprises the circuit substrate of claim 16 and a semiconductor chip mounted on the circuit substrate. A semiconductor device comprising the semiconductor chip package of claim 17. A semiconductor chip package comprises a semiconductor chip and a hardener for sealing the semiconductor chip, wherein the hardener is a hardener obtained from the resin composition of any one of claims 1 to 13. A semiconductor device comprising the semiconductor chip package of claim 19.