TW202210539A - Resin composition capable of obtaining a cured product with little warpage, high elasticity, and excellent adhesion to inorganic materials - Google Patents

Abstract

The present invention provides a resin composition or a resin paste capable of obtaining a cured product with little warpage, high elasticity, and excellent adhesion to inorganic materials, and being excellent strippability from film materials; a cured product, a resin sheet, a printed wiring board, a semiconductor chip pacage, a semiconductor device, a method for manufacturing the printed wiring board, and a method for manufacturing the semiconductor chip package. The resin composition includes (A) an epoxy resin, (B) a compound having a free radical, polymerizable, unsaturated group and a polyalkylene oxide structure and satisfying a specific condition, (C) an acid anhydride, (D) a free radical generating agent, and (E) an inorganic filler, meaning that [b]:[c] of the mass ratio of (B) component to (C) component ranges from 0.2:1 to 1.5:1.

Description

resin composition

The present invention relates to resin compositions. Furthermore, it relates to a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, a semiconductor device, a manufacturing method of a printed wiring board, and a manufacturing method of a semiconductor chip package.

In order to seal a printed wiring board or a semiconductor wafer including a semiconductor device, a liquid resin composition is used as a sealing material. Patent Document 1 discloses, as a sealing material, a liquid epoxy resin composition comprising (a) an epoxy resin, (b) a hardener, (c) a latent catalyst, (d) a A polymerizable monomer having two or more radically polymerizable double bonds, (e) a radical polymerization initiator, and (f) an inorganic filler (claim 22). Patent Document 2 discloses, as a sealing material, a liquid ring containing an epoxy resin that is liquid at room temperature, an amine hardener, a thermosetting acrylic resin, a thermal polymerization initiator for the above-mentioned thermosetting acrylic resin, and an inorganic filler Oxygen resin composition (claim 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-255864 [Patent Document 2] Japanese Patent Laid-Open No. 2014-094981

[The problem to be solved by the invention]

However, as a resin composition for compression molding (for compression molding), it is generally required to obtain a cured product with little warpage. In addition, from the viewpoint of improving the handling properties of printed wiring boards and semiconductor chip packages, the resulting cured product is required to have a high modulus of elasticity. However, the inventors of the present invention have studied and found that a cured product with small warpage tends to have a small elastic modulus. In addition, a cured product with a large elastic modulus tends to have a large warpage. Therefore, reducing the warpage and increasing the elastic modulus are in the relationship of the fold (first fold), and it is difficult to achieve both.

In addition, from the viewpoint of reliability, the cured product of the resin composition used as the sealing material is required to have the adhesion force (hereinafter also referred to as "inorganic material adhesion") with the inorganic material (such as silicon or copper) in contact with the cured product. ")high. On the other hand, the resin composition layer (compression-molded body) obtained by compression-molding the resin composition is required to be excellent in releasability from the release film (hereinafter also referred to as "film material releasability"). Here, the so-called release film generally refers to a film material having releasability used in compression molding. Since the release film is interposed between the resin composition layer and the mold during compression molding, direct contact between the resin composition layer and the mold is prevented, and therefore, it is expected that the resin composition layer can be easily removed after compression molding.

However, as a result of research by the inventors of the present invention, it was found that when there is high adhesion between the cured product of the resin composition and the inorganic material, there is usually a gap between the resin composition layer (compression molded body) of the resin composition and the release film. There is also a tendency for high-density adhesion (2nd fold). Therefore, after compression molding, it may be difficult to remove the resin composition layer from the mold, or even if the resin composition layer can be removed from the mold, it may be difficult to peel off the release layer from the resin composition layer.

Based on the above, for the resin composition for compression molding, it is required to reduce the warpage of the cured product and increase the elastic modulus of the cured product. The second folding punch with high peelability of the layer (compression-molded body) from the film material. If these folds can be resolved, handling of the resin composition layer (compression molded body) of the resin composition becomes easy, and for example, handling of a sealing body in which a semiconductor wafer is sealed with a cured product of the resin composition becomes easy.

The object of the present invention is to provide a resin composition or resin paste that can obtain a cured product with little warpage, a large elastic modulus, and excellent adhesion to inorganic materials, and is excellent in releasability to film materials; and to provide a resin composition using the resin composition. Cured products obtained from resin pastes or resin pastes, resin sheets, printed wiring boards, semiconductor chip packages, semiconductor devices, methods for manufacturing printed wiring boards, and methods for manufacturing semiconductor chip packages. [means to solve the problem]

As a result of intensive research, the present inventors found that the above-mentioned problems can be solved by including a specific component in a specific compounding amount in a resin composition, and thus completed the present invention.

(式(1)中，E表示自由基聚合性不飽和基之當量(g/eq.)，N表示分子中自由基聚合性不飽和基之數，且為1以上之整數)， (C)酸酐、(D)自由基產生劑，以及(E)無機填充材， 表示(B)成分相對於(C)成分之質量比的[b]:[c]於0.2:1~ 1.5:1之範圍內。 [2] 如[1]之樹脂組成物，其中(B)成分具有之聚環氧烷構造係以式：-(R^B O)_n -表示，前述式中，n為2以上之整數，R^B 分別獨立為可具有取代基之碳數1~6之伸烷基。 [3] 如[2]之樹脂組成物，其中複數R^B 中至少1個基R^B 包含伸乙基。 [4] 如[1]至[3]中任一項之樹脂組成物，其中(B)成分具有之自由基聚合性不飽和基係選自乙烯基、烯丙基、1-丁烯基、2-丁烯基、丙烯醯基、甲基丙烯醯基、富馬醯基、馬來醯基、乙烯基苯基、苯乙烯基及桂皮醯基之1種以上。 [5] 如[4]之樹脂組成物，其中(B)成分具有之自由基聚合性不飽和基包含選自甲基丙烯醯基及丙烯醯基之1種以上。 [6] 如[4]或[5]之樹脂組成物，其中(B)成分具有之自由基聚合性不飽和基包含甲基丙烯醯基。 [7] 如[1]至[6]中任一項之樹脂組成物，其中(B)成分包含選自式(1)中N為1之化合物及式(1)中N為2之化合物之1種以上的化合物。 [8] 如[7]之樹脂組成物，其中式(1)中N為1之化合物的分子量為150以上。 [9] 如[7]或[8]之樹脂組成物，其中式(1)中N為2之化合物的自由基聚合性不飽和基之當量(g/eq.)為500以上。 [10] 如[1]至[9]中任一項之樹脂組成物，其中(B)成分之自由基聚合性不飽和基之當量為4500g/eq.以下。 [11] 如[1]至[10]中任一項之樹脂組成物，其中(B)成分之含量，於將樹脂組成物中不揮發成分中(E)無機填充材以外之成分設為100質量%時，為10質量%以上40質量%以下。 [12] 如[1]至[11]中任一項之樹脂組成物，其中將(C)成分之量(g)除以該(C)成分具有之酸酐基之當量(g/eq.)之值的合計相對於將(A)成分之量(g)除以該(A)成分具有之環氧基之當量(g/eq.)之值的合計之當量比(c)/(a)之值為0.4以上。 [13] 如[1]至[12]中任一項之樹脂組成物，其中(D)成分係選自10小時半衰期溫度T10(℃)為50℃以上110℃以下之範圍內之自由基產生劑之1種以上。 [14] 如[1]至[13]中任一項之樹脂組成物，其中(E)成分之含量，於將樹脂組成物中不揮發成分含量設為100質量%時，為70質量%以上。 [15] 如[1]至[14]中任一項之樹脂組成物，其係壓縮成形用。 [16] 如[15]之樹脂組成物，其中(D)成分係選自壓縮成形時之模具溫度Tc(℃)與該(D)成分之10小時半衰期溫度T10(℃)之差ΔT(℃)為20℃以上80℃以下之範圍內之自由基產生劑之1種以上。 [17] 如[1]至[16]中任一項之樹脂組成物，其係絕緣層形成用。 [18] 一種樹脂膏，其包含如[1]至[17]中任一項之樹脂組成物。 [19] 一種硬化物，其係如[1]至[17]中任一項之樹脂組成物或如[18]之樹脂膏的硬化物。 [20] 一種樹脂薄片，其具有支撐體，及設於該支撐體上之包含如[1]至[17]中任一項之樹脂組成物或如[18]之樹脂膏的樹脂組成物層。 [21] 一種印刷配線板，其包含藉由如[1]至[17]中任一項之樹脂組成物或如[18]之樹脂膏的硬化物形成之絕緣層。 [22] 一種半導體晶片封裝，其包含如[21]之印刷配線板及搭載於該印刷配線板之半導體晶片。 [23] 一種半導體晶片封裝，其包含半導體晶片及密封該半導體晶片之如[1]至[17]中任一項之樹脂組成物或如[18]之樹脂膏的硬化物。 [24] 一種半導體裝置，其包含如[21]之印刷配線板或如[22]或[23]之半導體晶片封裝。 [25] 一種印刷配線板之製造方法，其包含 於電路基板上，藉由壓縮成形法形成包含如[1]至[17]中任一項之樹脂組成物之樹脂組成物層或包含如[18]之樹脂膏的樹脂組成物層之步驟，及使前述樹脂組成物層硬化之步驟。 [26] 一種半導體晶片封裝之製造方法，其包含於半導體晶片上，藉由壓縮成形法形成包含如[1]至[17]中任一項之樹脂組成物之樹脂組成物層或包含如[18]之樹脂膏的樹脂組成物層之步驟，及使前述樹脂組成物層硬化之步驟。 [發明效果]That is, the present invention includes the following. [1] A resin composition comprising (A) an epoxy resin, (B) a compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure in the molecule, and satisfying the following formula (1) compound,

(In formula (1), E represents the equivalent of radically polymerizable unsaturated groups (g/eq.), and N represents the number of radically polymerizable unsaturated groups in the molecule, and is an integer of 1 or more), (C) Acid anhydride, (D) radical generator, and (E) inorganic filler, [b]:[c] representing the mass ratio of (B) component to (C) component is in the range of 0.2:1 to 1.5:1 Inside. [2] The resin composition according to [1], wherein the polyalkylene oxide structure of the component (B) is represented by the formula: -(R ^B O) _n -, wherein n is an integer of 2 or more, and R ^B is each independently an alkylene group having 1 to 6 carbon atoms which may have a substituent. [3] The resin composition according to [2], wherein at least one group R ^{B of the plurality of R B contains} an ethylidene group. [4] The resin composition according to any one of [1] to [3], wherein the radically polymerizable unsaturated group possessed by the component (B) is selected from the group consisting of vinyl, allyl, 1-butenyl, One or more of 2-butenyl, acryl, methacryloyl, fumaric, maleic, vinylphenyl, styryl and cinnamonyl. [5] The resin composition according to [4], wherein the radically polymerizable unsaturated group possessed by the component (B) includes at least one selected from the group consisting of a methacryloyl group and an acryl group. [6] The resin composition according to [4] or [5], wherein the radically polymerizable unsaturated group possessed by the component (B) contains a methacryloyl group. [7] The resin composition according to any one of [1] to [6], wherein the component (B) comprises a compound selected from the group consisting of compounds in which N is 1 in formula (1) and compounds in which N is 2 in formula (1). 1 or more compounds. [8] The resin composition according to [7], wherein the compound in which N is 1 in the formula (1) has a molecular weight of 150 or more. [9] The resin composition according to [7] or [8], wherein the compound in which N is 2 in the formula (1) has an equivalent weight (g/eq.) of radically polymerizable unsaturated groups of 500 or more. [10] The resin composition according to any one of [1] to [9], wherein the equivalent weight of the radically polymerizable unsaturated group of the component (B) is 4500 g/eq. or less. [11] The resin composition according to any one of [1] to [10], wherein the content of the (B) component is 100 in the non-volatile components in the resin composition other than the (E) inorganic filler. In mass %, it is 10 mass % or more and 40 mass % or less. [12] The resin composition according to any one of [1] to [11], wherein the amount (g) of the component (C) is divided by the equivalent weight (g/eq.) of the acid anhydride group that the component (C) has. The equivalence ratio (c)/(a) of the sum of the values to the sum of the value of the amount (g) of the component (A) divided by the equivalent weight (g/eq.) of the epoxy group contained in the component (A) The value is 0.4 or more. [13] The resin composition according to any one of [1] to [12], wherein the component (D) is selected from free radical generation within the range of a 10-hour half-life temperature T10 (°C) of 50°C or higher and 110°C or lower 1 or more of the agents. [14] The resin composition according to any one of [1] to [13], wherein the content of the component (E) is 70% by mass or more when the nonvolatile content in the resin composition is 100% by mass . [15] The resin composition according to any one of [1] to [14], which is for compression molding. [16] The resin composition according to [15], wherein the (D) component is selected from the difference ΔT (°C) between the mold temperature Tc (°C) during compression molding and the 10-hour half-life temperature T10 (°C) of the (D) component ) is one or more types of radical generators in the range of 20°C or higher and 80°C or lower. [17] The resin composition according to any one of [1] to [16], which is for forming an insulating layer. [18] A resin paste comprising the resin composition according to any one of [1] to [17]. [19] A hardened product, which is a hardened product of the resin composition according to any one of [1] to [17] or the resin paste according to [18]. [20] A resin sheet having a support, and a resin composition layer comprising the resin composition of any one of [1] to [17] or the resin paste of [18] provided on the support . [21] A printed wiring board comprising an insulating layer formed of the resin composition according to any one of [1] to [17] or a hardened product of the resin paste according to [18]. [22] A semiconductor chip package comprising the printed wiring board according to [21] and a semiconductor chip mounted on the printed wiring board. [23] A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of [1] to [17] or the resin paste according to [18] that seals the semiconductor chip. [24] A semiconductor device comprising a printed wiring board as in [21] or a semiconductor chip package as in [22] or [23]. [25] A method for manufacturing a printed wiring board, comprising, on a circuit board, forming a resin composition layer comprising the resin composition according to any one of [1] to [17] or a resin composition layer comprising the resin composition according to [1] to [17] on a circuit board. 18] The step of forming the resin composition layer of the resin paste, and the step of hardening the above-mentioned resin composition layer. [26] A method of manufacturing a semiconductor chip package, comprising, on a semiconductor chip, forming a resin composition layer comprising the resin composition according to any one of [1] to [17] or a resin composition layer comprising the resin composition according to [1] to [17] on a semiconductor wafer. 18] The step of forming the resin composition layer of the resin paste, and the step of hardening the above-mentioned resin composition layer. [Inventive effect]

According to the present invention, it is possible to provide a resin composition or resin paste that can obtain a cured product with little warpage, a large elastic modulus, and excellent adhesion to inorganic materials, and is excellent in releasability to film materials; and a resin composition using the resin composition. Cured products obtained from resin pastes or resin pastes, resin sheets, printed wiring boards, semiconductor chip packages, semiconductor devices, methods for manufacturing printed wiring boards, and methods for manufacturing semiconductor chip packages.

Hereinafter, the resin composition, resin paste, cured product, resin sheet, printed wiring board, semiconductor chip package, semiconductor device, manufacturing method of printed wiring board, and manufacturing method of semiconductor chip package of the present invention will be described in detail.

[resin composition] The resin composition of the present invention includes (A) an epoxy resin, (B) a compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure and satisfying specific conditions, (C) an acid anhydride, and (D) a radical generator , and (E) the inorganic filler, the [b]:[c] representing the mass ratio of the (B) component to the (C) component is in the range of 0.2:1 to 1.5:1. According to this resin composition, a cured product with small warpage, high elastic modulus, and excellent adhesion to inorganic materials can be obtained, and the effect of excellent releasability to film materials can be exhibited. By using these resin compositions, a resin paste, a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device that can exhibit this effect can be provided.

The resin composition of this invention is a combination of (A) component, (B) component, (C) component, (D) component, and (E) component, and may further contain arbitrary components. Examples of optional components include (F) a curing accelerator, (G) compounds having a radically polymerizable unsaturated group (excluding compounds having a polyalkylene oxide structure), and (H) other additives. Hereinafter, each component contained in the resin composition will be described in detail. Furthermore, in the present invention, the content of each component in the resin composition is a value when the nonvolatile content in the resin composition is 100% by mass unless otherwise specified.

<(A) Epoxy resin> The resin composition of the present invention contains (A) an epoxy resin. The epoxy resin refers to a resin having one or more epoxy groups in the molecule. Since the resin composition contains the (A) epoxy resin, a cured product having a cross-linked structure can be obtained.

Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bicyclic epoxy resin Pentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tertiary butylcatechol type epoxy resin, naphthalene type epoxy resin, Naphthol type epoxy resin, Anthracene type epoxy resin, Glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, Cresol novolac type epoxy resin, Biphenyl type epoxy resin, Chain aliphatic ring Oxygen resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type ring Oxygen resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin; tetraphenylethane type epoxy resin, alkylene oxide type epoxy resin, etc. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

It is preferable that (A) component contains the epoxy resin which has two or more epoxy groups in a molecule|numerator. When the nonvolatile content of (A) component is 100 mass %, it is usually 50 mass % or more, preferably 60 mass % or more, more preferably 70 mass % or more is an epoxy resin having two or more epoxy groups in the molecule.

The epoxy resin may be (A-1) liquid epoxy resin or (A-2) solid epoxy resin. The resin composition may contain (A-1) liquid epoxy resin and (A-2) solid epoxy resin in combination. From the viewpoint of obtaining a resin composition having excellent fluidity at the time of molding, the component (A) is preferably (A-1) a liquid epoxy resin. Component (A) may further contain (A-2) solid epoxy resin as necessary.

((A-1) Liquid epoxy resin) The so-called (A-1) liquid epoxy resin is an epoxy resin that is liquid at a temperature of 20°C. The resin composition preferably contains (A-1) a liquid epoxy resin.

As a liquid epoxy resin, the epoxy resin which has two or more epoxy groups in a molecule|numerator is preferable, and the aromatic liquid epoxy resin which has two or more epoxy groups in a molecule|numerator is more preferable. In this specification, the epoxy resin of an aromatic type means the epoxy resin which has an aromatic ring in the molecule|numerator.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidol type epoxy resin are preferable Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidylamine type epoxy resin , alkylene oxide type epoxy resin and epoxy resin with butadiene structure, more preferably bisphenol A type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin.

Specific examples of liquid epoxy resins include "YX7400" manufactured by Mitsubishi Chemical Corporation; "HP4032", "HP4032D", "HP-4032-SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; Mitsubishi Chemical Corporation "828US", "jER828EL", "825", "828EL" (bisphenol A epoxy resin) manufactured by the company; "jER807", "1750" (bisphenol F epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "EP3950L" (glycidylamine type epoxy resin manufactured by ADEKA Corporation) type epoxy resin); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "EX-721" manufactured by NAGASE CHEMTEX Co., Ltd. (shrinkage Glycerol ester epoxy resin); "CELLOXIDE 2021P" made by DAICEL (alicyclic epoxy resin with ester skeleton); "PB-3600" made by DAICEL (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd. These may be used individually by 1 type, and may be used in combination of 2 or more types. As exemplified by the examples to be described later, one or more liquid forms selected from "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "HP-4032-SS" manufactured by DIC Corporation, and "630LSD" manufactured by Mitsubishi Chemical Corporation were used. Epoxy resin is one of the preferred aspects. From the viewpoint of reducing the warpage of the cured body, more preferably two or more kinds selected from "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation, "HP-4032-SS" manufactured by DIC Corporation, and "630LSD" manufactured by Mitsubishi Chemical Corporation liquid epoxy resin. In addition, from the viewpoint of reducing the warpage of the cured product, it is also preferable to use "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation, "HP-4032-SS" manufactured by DIC Corporation, and "630LSD" manufactured by Mitsubishi Chemical Corporation. Two or more kinds are used as liquid epoxy resins.

The content of the component (A-1) in the resin composition is based on the viewpoint of obtaining the effect of containing the component (A-1) (for example, the workability (fluidity during molding) of the resin composition is improved, and the compatibility is improved), From the viewpoint of obtaining a cured product with less warpage, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass % or more, particularly preferably 5 mass % or more. The upper limit of the content of the component (A-1) is not particularly limited as long as the effect of the present invention is not excessively impaired, but it is, for example, 30 mass % or less or 25 mass % or less, from the viewpoint of obtaining a cured product with a high elastic modulus, It may be 20 mass % or less or 15 mass % or less.

((A-2) Solid epoxy resin) The solid epoxy resin means an epoxy resin that is solid at a temperature of 20°C. The resin composition may contain only (A-1) liquid epoxy resin as component (A), but from the viewpoint of improving the crosslinking density, it is also preferable to combine with (A-1) liquid epoxy resin and contain ( A-2) Solid epoxy resin. As a solid epoxy resin, the solid epoxy resin which has three or more epoxy groups in a molecule|numerator is preferable.

The solid epoxy resin is preferably a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolac type epoxy resin, and a dicyclopentadiene type epoxy resin Resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin Resin, tetraphenylethane type epoxy resin, more preferably naphthol type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin and biphenyl type epoxy resin.

Specific examples of solid epoxy resins include "HP4302H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation ; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200L" manufactured by DIC Corporation , "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA" manufactured by DIC Corporation -7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; new "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumitkin Chemical Co., Ltd.; "ESN485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YX4000", "YL6121" (biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation ; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "157S70" (bisphenol A novolac epoxy resin) manufactured by Mitsubishi Chemical Corporation; AF type epoxy resin); "YL7800" (Fine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" manufactured by Mitsubishi Chemical Corporation ( Tetraphenylethane type epoxy resin) etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the component (A-2) in the resin composition may be 0% (ie, not included) when the non-volatile matter in the resin composition is 100% by mass, but (A-2) is included on the basis of obtaining From the viewpoint of the effect due to the component (for example, from the viewpoint of reducing the average linear thermal expansion coefficient, improving heat resistance, or having a good crosslinking density), it is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and still more preferably 0.1 mass % Above, particularly preferably 0.2 mass % or more. The upper limit of the content of the component (A-2) is preferably less than the content of the component (A-1). (A-2) The upper limit of the content of the component can be 10 mass % or less, 5 mass % or less, and 3 mass % when the nonvolatile content in the resin composition is 100 mass % from the viewpoint of moderately suppressing the crosslinking density. or less or less than 1 mass %.

When (A-1) liquid epoxy resin and (A-2) solid epoxy resin are used together as component (A), the ratio of these amounts (liquid epoxy resin: solid epoxy resin) is based on the mass ratio. It is preferably in the range of 1:0.01~1:0.8. By making the amount ratio of (A-1) liquid epoxy resin to (A-2) solid epoxy resin within this range, i) moderate fluidity can be imparted during molding, ii) resin composition can be obtained In the form of use, the handleability is improved, and iii) a hardened product with sufficient breaking strength can be obtained. From the viewpoint of obtaining the effects of i) to iii) above and the viewpoint of moderately suppressing the crosslinking density, the amount ratio of (A-1) liquid epoxy resin to (A-2) solid epoxy resin (liquid epoxy resin) Resin: solid epoxy resin) is the range of 1:0.01-1:0.5 in mass ratio, More preferably, it is the range of 1:0.01-1:0.1.

The epoxy equivalent of the epoxy resin of the component (A) is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., still more preferably 70g/eq.~2000g/eq. ., and more preferably 70g/eq.~ 1000g/eq.. By making it into this range, the crosslinking density of hardened|cured material can be made sufficient, and the hardened|cured material excellent in heat resistance can be obtained. In addition, the epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of epoxy groups.

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the component (A) in the resin composition is preferably 1 mass % or more, more preferably 2 mass % when the non-volatile content in the resin composition is 100 mass % from the viewpoint of improving the intended effect of the present invention. The above, more preferably 3 mass % or more, particularly preferably 5 mass % or more. The upper limit of the content of the component (A) is not particularly limited as long as it does not unduly impair the effect of the present invention. 20 mass % or less or 15 mass % or less.

The content of the component (A) is preferably 10% by mass or more when the components other than the (E) inorganic filler in the nonvolatile components in the resin composition are set to 100% by mass from the viewpoint of improving the intended effect of the present invention, More preferably, it is 15 mass % or more, still more preferably 20 mass % or more, and particularly preferably 25 mass % or more. The upper limit of the content of the component (A) is not particularly limited as long as it does not unduly impair the effect of the present invention. It may be 50 mass % or less, 48 mass % or less, or 45 mass % or less.

The content (mass) of the component (A) in the resin composition is preferably at least one-fifth of the total (mass) of the content of the component (B) and the content of the component (C) from the viewpoint of improving the intended effect of the present invention. , more preferably more than one quarter, and more preferably more than three tenths. The percentage of the value [a]/(b]+[c]) of the content of the component (A) in the resin composition relative to the total mass ratio of the content of the (B) component and the content of the (C) component, preferably It is 20 mass % or more, More preferably, it is 25 mass % or more, More preferably, it is 30 mass % or more. The upper limit of the percentage of the value of the mass ratio [a]/([b]+[c]) may be 100 mass % or less, 90 mass % or less, or 80 mass % or less from the viewpoint of further enhancing the expected effect of the present invention.

<(B) A compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure and satisfying specific conditions> The resin composition of the present invention contains (B) a compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure, and a compound satisfying specific conditions (hereinafter also referred to as "radical-reactive polyRO compound of the present invention") . The radical-reactive polyRO compound of this invention can use 2 or more types. The resin composition contains the component (B) in combination with the component (A) and the component (C), and the component (B) contributes to the expected effects of the present invention (warpage, inorganic material adhesion, elastic modulus, and film material). At least a part of the peelability), especially the flexibility due to the alkylene oxide structure, is considered to greatly contribute to the reduction of the warpage of the cured product and the improvement of the adhesiveness of the inorganic material.

The radically polymerizable unsaturated group which the component (B) has is exemplified by a group containing an ethylenic carbon-carbon double bond. Specific examples include vinyl, allyl, 1-butenyl, 2-butenyl, acryl, methacryloyl, fumaric, maleic, vinylphenyl, benzene One or more of vinyl group and cinnamon group. The component (B) may contain two or more radically polymerizable unsaturated groups in one molecule. The radically polymerizable unsaturated group possessed by the component (B) preferably contains at least one selected from the group consisting of a methacryloyl group and an acryl group from the viewpoint of improving the reactivity, and more preferably contains from the viewpoint of controlling the reactivity Methacryloyl. In addition, it is preferable that (B) component has a radically polymerizable unsaturated group at a molecular terminal from a viewpoint of obtaining the hardened|cured material with little warpage.

(式(1)中，E表示自由基聚合性不飽和基之當量(g/eq.)，N表示分子中自由基聚合性不飽和基之數，且為1以上之整數)。所謂自由基聚合性不飽和基之當量係包含1當量之自由基聚合性不飽和基的樹脂之質量。藉由滿足此條件，可發揮本發明預期效果。N可為例如5以下、4以下或3以下。The specific condition that the so-called (B) component should satisfy is the following formula (1):

(In formula (1), E represents the equivalent weight (g/eq.) of radically polymerizable unsaturated groups, and N represents the number of radically polymerizable unsaturated groups in the molecule, and is an integer of 1 or more). The equivalent of the radically polymerizable unsaturated group refers to the mass of the resin containing 1 equivalent of the radically polymerizable unsaturated group. By satisfying this condition, the intended effect of the present invention can be exhibited. N may be, for example, 5 or less, 4 or less, or 3 or less.

The above formula (1) means that the molecular weight per equivalent (corresponding to the term "E/N" in the formula (1)) must be sufficiently large corresponding to the number N of radically polymerizable unsaturated groups. Specifically, when N is 1, the above formula (1) means that the molecular weight of the compound must be 150 or more, and when N is 2, it means the equivalent of the radical polymerizable unsaturated group of the compound (g/eq.) It must be 500 or more (that is, the molecular weight is 1000 or more). Therefore, by making the molecular weight per equivalent molecular weight of the component (B) larger according to the number of radically polymerizable unsaturated groups, it is considered that the increase in warpage due to the influence of the curing shrinkage of the resin composition can be suppressed. tendency.

The component (B) includes, for example, at least one compound selected from the group consisting of the compound in which N is 1 in formula (1) and the compound in which N is 2 in formula (1). Here, the compound in which N in the formula (1) is 1 is a compound having a molecular weight of 150 or more as described above. Similarly, the compound in which N in the formula (1) is 2 is a compound in which the equivalent weight (g/eq.) of the radically polymerizable unsaturated group is 500 or more.

When the component (B) is a compound in which N is 1 in the above formula (1), the equivalent weight of the radically polymerizable unsaturated group may be 150 g/eq. or more, and the lower limit may be 250 g/eq. or more or 400 g/eq. or more . When the component (B) is a compound in which N is 2 in the above formula (1), the equivalent weight of the radically polymerizable unsaturated group may be 500 g/eq. or more, and the lower limit may be 510 g/eq. or more or 600 g/eq. or more . From the viewpoint of improving the expected effect of the present invention, the upper limit of the equivalent weight of the radically polymerizable unsaturated group of the radically reactive polyRO compound of the present invention may be 4500 g/eq. or less. From the viewpoint of improving the fluidity of the resin composition (the viscosity of the resin composition or the filling property of the inorganic filler), the upper limit of the equivalent weight of the radically polymerizable unsaturated group is preferably 3000 g/eq. or less, more preferably 2000 g/ eq. or less, and more preferably 1500 g/eq. or less. When the resin composition contains plural types of the radically reactive polyRO compounds of the present invention as the component (B), the equivalent weight of the radically polymerizable unsaturated groups of each compound preferably satisfies the above range.

The polyalkylene oxide structure that the component (B) has is represented by the formula (2): -(R ^B O) _n - in this embodiment, wherein in the formula (2), n is an integer of 2 or more, R and ^B are each independently an alkylene group having 1 to 6 carbon atoms which may have a substituent. The component (B) contains at least one polyalkylene oxide structure in one molecule, and is preferably a polyalkylene oxide structure containing two or more polyalkylene oxide structures in one molecule from the viewpoint of obtaining a cured product excellent in adhesion to inorganic materials. In this case, the plural polyalkylene oxide structures may be the same or different from each other. When the radical-reactive polyRO compound of the present invention includes plural polyalkylene oxide structures that are the same or different from each other, the number of repetitions of the alkylene oxide structure per molecule (hereinafter also referred to as "RO number") represents each ring The sum of the numerical values represented by n in the formula (2) of the oxane structure is represented. That is, the number of RO means the number of the divalent group ^R BO in the above formula (2) contained in 1 molecule of the radical-reactive polyRO compound of the present invention.

In the above formula (2), from the viewpoint of obtaining a cured product excellent in adhesion, n is 2 or more, preferably 4 or more, more preferably 9 or more, and still more preferably an integer of 11 or more. From the viewpoint of improving the fluidity of the resin composition (viscosity of the resin composition or filling property of the inorganic filler), n is usually 101 or less, preferably 90 or less, more preferably 68 or less, and more preferably 65 or less. Integer.

In the above formula (2), the carbon number of the alkylene group contained in R ^B is usually 1 to 6, and the adhesion to inorganic materials is obtained by increasing the content ratio of oxygen atoms as polar parts contained in the polyalkylene oxide structure. From the viewpoint of an excellent cured product, preferably 1 to 5, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 to 2, based on the reduction of warpage due to the influence of curing shrinkage. From the viewpoint of the hardened product, it is preferably 2 to 5, more preferably 2 to 4, and still more preferably 2 to 3. In the above formula (2), the carbon number of the alkylene group contained in R ^B is based on the viewpoint of obtaining a cured product with excellent adhesion to inorganic materials and a cured product with reduced warpage due to the influence of curing shrinkage. point of view, typically 2 is the best. Therefore, in the above formula (2), among the plurality of groups ^RB , at least one group ^RB includes an ethylidene group.

In the above formula (2), the alkylene group contained in R ^B usually does not have a substituent, but may have a substituent. Examples of such substituents include alkylene groups having 1 to 3 carbon atoms, halogen atoms, -OH, -OC _1-5 alkyl groups, -N(C _1-5 alkyl groups) ₂ , C _{1- 5} alkyl, C _6-10 aryl, -NH ₂ , -CN, -C(O)OC _1-5 alkyl, -COOH, -C(O)H, epoxy, -NO ₂ and the like. These substituents are preferably an epoxy group, -OH, -NH ₂ and -COOH from the viewpoint of improving the reactivity with the (A) component and/or (C) component. In addition, when the radically reactive polyRO compound of the present invention has an epoxy group in the molecule, it is classified as a compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure and satisfying the above-mentioned specific conditions. It is (B) component. In this way, the radical-reactive poly-RO compound of the present invention preferably contains a group reactive with the (A) component and/or (C) component, and also preferably contains a reactive group with the (A) component, thereby A cross-linked structure can be formed, and a cured product with high elastic modulus and excellent handleability can be obtained. In this case, one or more types of radical-reactive poly-RO compounds containing a group having reactivity with the (A) component and/or (C) component may be used in combination with a ) one or more kinds of radical-reactive poly-RO compounds having a reactive group as a component. Furthermore, from the viewpoint of obtaining a cured product with a low dielectric loss factor, it is preferable to exclude a halogen atom from the substituent which the alkylene group contained in R ^B has. The substituent may be contained alone or in combination of two or more.

Specific examples of the polyalkylene oxide structure possessed by the component (B) include a polyethylene oxide structure (-(C ₂ H ₄ O) _n -; where n is the same as n in the formula (2)), polycyclic Oxypropane structure (-(C ₃ H ₆ O) _n -; where n is the same as n in formula (2)), poly-n-butylene oxide structure (-(C ₄ H ₈ O) _n -; where n is the same as n of formula (2) is the same), poly(ethylene oxide-copolymerization-propylene oxide) structure, poly(ethylene oxide-non-returnable copolymerization-propylene oxide) structure, poly(ethylene oxide-alternating copolymerization) - propylene oxide) structure and poly(ethylene oxide-block copolymer-propylene oxide) structure. Among them, the polyalkylene oxide structure that the component (B) has is preferably any one of the above-mentioned polyethylene oxide structure and the above-mentioned polypropylene oxide structure from the viewpoint of obtaining a cured product excellent in the adhesion of the inorganic material. , more preferably the above-mentioned polyethylene oxide structure. However, from the component (B), the epoxy resin which has an alkylene oxide structure is excluded.

When the radical-reactive polyRO compound of the present invention contains one or a plurality of polyethylene oxide structures in one molecule, the number of repetitions of the ethylene oxide structures per molecule (hereinafter, also referred to as "EO number") ) is 2 or more, from the viewpoint of obtaining a cured product with excellent adhesion, preferably 4 or more, more preferably more than 9 or more, more preferably an integer of 11 or more, usually 101 or less, based on improving the resin composition From the viewpoint of the fluidity of the material (the viscosity of the resin composition or the filling property of the inorganic filler), it is preferably an integer of 90 or less, more preferably 68 or less, and still more preferably 65 or less. The EO number means the number when the divalent group R ^B O in the above formula 1 contained in one molecule of the radical-reactive polyRO compound of the present invention is represented by -(C ₂ H ₄ O)-. The PO number means the number when the divalent group R ^B O in the above formula 1 contained in one molecule of the radical-reactive polyRO compound of the present invention is represented by -(C ₃ H ₆ O)-.

Specific examples of the component (B) include vinyl, allyl, 1-butenyl, 2-butenyl, acryl, methacryloyl, fumaric, and maleic , one or more radically polymerizable unsaturated groups selected from the group consisting of vinylphenyl, styryl and cinnamonyl, and a structure selected from polyethylene oxide (-(C ₂ H ₄ O) _n -; wherein n is the same as the formula (2) where n is the same), polypropylene oxide structure (-(C ₃ H ₆ O) _n -; where n is the same as n in formula (2)), poly-n-butylene oxide structure (-(C ₄ H ₈ O) _n -; wherein, n is the same as n in the formula (2)), poly(ethylene oxide-co-propylene oxide) structure, poly(ethylene oxide-non-returnable copolymer-epoxy Propane) structure, poly(ethylene oxide-alternating copolymer-propylene oxide) structure and poly(ethylene oxide-block copolymer-propylene oxide) structure are polyalkylene oxide structures that satisfy the above formula (1) the compound. From the viewpoint of obtaining a cured product excellent in heat resistance, the component (B) preferably contains one or more monovalent or divalent aromatic hydrocarbon groups in the molecule, and preferably contains two or more monovalent or divalent aromatic hydrocarbon groups in the molecule. A divalent aromatic hydrocarbon group. As a monovalent or divalent aromatic hydrocarbon group, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenylene group, a 1-naphthylene group, a 2-naphthylene group, and the like are exemplified. Two or more monovalent or divalent aromatic hydrocarbon groups may be bonded to each other directly or via a linking group, and by such bonding, for example, a bisphenol structure, preferably a bisphenol A structure, may be formed.

As (B) component, a commercial item can be used. Examples of commercially available products include monofunctional acrylates "AM-90G" (number of EO: 9), "AM-130G" (number of EO: 13), "AMP-20GY" (number of EO) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. : 2), bifunctional acrylate "A-1000" (EO number: 23), "A-B1206PE" (EO number: 6, PO number: 12, RO number: 18), "A-BPE-20" ( EO number: 17), "A-BPE-30" (EO number: 30); monofunctional methacrylate "M-20G" (EO number: 2), "M-40G" (EO number: 4), "M-90G" (EO number: 9), "M-130G" (EO number: 13), "M-230G" (EO number: 23); and bifunctional methacrylate "23G" (EO number: 23) 23), "BPE-900" (EO number: 17), "BPE-1300N" (EO number: 30), "1206PE" (EO number: 6, RO number: 18), and Gongrongsha Chemical Co., Ltd. "LIGHT ESTER BC" (number of EOs: 2), "LIGHT ESTER 041MA" (number of EOs: 30), "LIGHT ACRYLATE EC-A" (number of EOs: 2), "LIGHT ACRYLATE EHDG-AT" (number of EOs: 18), "FA-023M" manufactured by Hitachi Chemical Corporation, "BLEMMER (registered trademark) manufactured by NOF Corporation" PME-4000" (number of EO: 90), "BLEMMER (registered trademark) 50POEO-800B" (number of EO: 8, number of PO: 7), "BLEMMER (registered trademark) PLE-200" (number of EO: 4), , "BLEMMER (registered trademark) PLE-1300" (EO number: 30), "BLEMMER (registered trademark) PSE-1300" (EO number: 30), "BLEMMER (registered trademark) 43PAPE-600B" (EO number: 6 , PO number: 6), "BLEMMER (registered trademark) ANP-300" (PO number: 5), etc. Among them, from the viewpoint of improving the expected effect of the present invention, for example, one selected from the group consisting of "M-230G", "M-130G", "23G", "M-40G", "M-90G" and "BPE-1300N" can be used. 1 or more commercially available products.

The molecular weight of the radically reactive polyRO compound of the present invention, in the compound in which N is 1 in formula (1), is 150 or more, and may be 250 or more or 400 or more. (B) The molecular weight of the radical-reactive poly-RO compound of the present invention, the compound in which N is 2 in formula (1), is 1000 or more, and may be 1020 or more or 1200 or more. From the viewpoint of improving the fluidity of the resin composition (the viscosity of the resin composition or the filling property of the inorganic filler), the upper limit of the molecular weight of the radical-reactive poly-RO compound of the present invention is, for example, 5,000 or less, preferably 3,000 or less, and more It is preferably 2,500 or less, more preferably 2,000 or less, and still more preferably 1,500 or less. When the component (B) is a commercially available product, the molecular weight as its nominal value is preferably within the above-mentioned range. When the component (B) is a polymer, the weight average molecular weight or the number average molecular weight is preferably within the above range. Here, when the component (B) is a polymer, the weight average molecular weight or number average molecular weight is the weight average molecular weight or number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The content of the component (B) is not particularly limited as long as the mass ratio of the component (B) to the component (C) is within the range described later, but when the nonvolatile content in the resin composition is set to 100% by mass, it is based on From the viewpoint of improving the expected effect of the present invention, it is 0.1 mass % or more, 0.2 mass % or more, or 0.3 mass % or more, and based on the viewpoint of further improving the expected effect of the present invention, it is preferably 1 mass % or more, more preferably 1.5 mass % or more, Still more preferably, it is 2 mass % or more. The upper limit is not particularly limited, but may be, for example, 20 mass % or less and 15 mass % or less, and preferably less than the content of the component (A) when the nonvolatile content in the resin composition is 100 mass %.

The content of the (B) component is not limited as long as the mass ratio of the (B) component to the (C) component is within the range described later, and the components other than the (E) inorganic filler in the nonvolatile components in the resin composition are set as When it is 100 mass %, from the viewpoint of improving the expected effect of the present invention, it is preferably 10 mass % or more, more preferably 13 mass % or more, still more preferably 15 mass % or more, and particularly preferably 16 mass % or more. The upper limit is not particularly limited, but from the viewpoint of improving the expected effect of the present invention, it is preferably 40 mass % or less, more preferably 39 mass % or less, and more preferably 38 mass % or less, based on the ability to obtain a cured product with a higher elastic modulus. From a viewpoint, it may be 35 mass % or less or 30 mass % or less.

<(C) Acid anhydride> The resin composition contains (C) acid anhydride. Acid anhydride refers to a compound having an acid anhydride group. Component (C) may be an acid anhydride that is liquid at a temperature of 20°C (hereinafter also referred to as "liquid acid anhydride") or an acid anhydride that is solid at a temperature of 20°C (hereinafter also referred to as "solid acid anhydride"). , or a combination of these. From the viewpoint of improving the fluidity of the resin composition (the viscosity of the resin composition or the filling property of the inorganic filler), the component (C) is preferably a liquid acid anhydride. (C)component may further contain a solid acid anhydride as needed. By containing (C) component in combination with (A) component and (B) component in the resin composition, (C) component contributes to the expected effects of the present invention (warpage, inorganic material adhesion, elastic modulus, and film material). At least a part of peelability), especially as illustrated in the column of Examples, when the resin composition contains the component (C), there is a tendency that the releasability of the film material is excellent.

The (C) acid anhydride reacts with the (A) component to harden the resin composition. Specific examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, Methyl nadic acid (nadic acid) anhydride, hydrogenated methyl naltic acid anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro- 3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, Naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene and Styrene made from acid copolymerization. Polymeric anhydrides of maleic acid resins, etc.

Examples of commercially available acid anhydrides include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Nippon Chemical Corporation, and "YH-306" manufactured by Mitsubishi Chemical Corporation. ", "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Chemical Corporation, etc.

In the present invention, from the viewpoint of exhibiting the intended effects of the present invention, [b]:[c] representing the mass ratio of the component (B) to the component (C) is in the range of 0.2:1 to 1.5:1, preferably Within the range of 0.25:1 to 1.35:1, more preferably within the range of 0.3:1 to 1.3:1.

The sum of the value of dividing the amount (g) of the component (C) by the equivalent weight (g/eq.) of the acid anhydride group that the component (C) has is relative to the amount (g) of the component (A) divided by the (A) The value of the ratio (equivalent ratio) (c)/(a) to the sum of the values of the equivalents (g/eq.) of the epoxy groups possessed by the component is preferably 0.4 or more from the viewpoint of exerting the intended effect of the present invention, and more Preferably it is 0.5 or more, more preferably 0.6 or more, and from the viewpoint of obtaining a cured product with little warpage, preferably 1.6 or less, more preferably 1.5 or less, still more preferably 1.4 or less.

The fat content of the component (C) is not limited as long as the mass ratio of the component (B) to the component (C) is within the above range, and the components other than the (E) inorganic filler in the nonvolatile components in the resin composition are set as When it is 100 mass %, it can be 10 mass % or more or 15 mass % or more from the viewpoint of improving the expected effect of the present invention. From the viewpoint of obtaining a resin composition layer (compression-molded body) excellent in film releasability, the content of the (C) component is 100 components other than the (E) inorganic filler in the nonvolatile components in the resin composition. In the case of mass %, it is preferably 17 mass % or more, more preferably 20 mass % or more, and still more preferably 23 mass % or more. The upper limit is not particularly limited, but may be, for example, 60 mass % or less. From the viewpoint of improving the intended effect of the present invention, it is preferably 58 mass % or less, more preferably 55 mass % or less, from the viewpoint of obtaining a cured product with less warpage. , may be 49 mass % or less or 48 mass % or less.

The content of the component (C) is not limited as long as the mass ratio of the component (B) to the component (C) is within the above range. However, when the nonvolatile content in the resin composition is set to 100% by mass, it is expected to improve the present invention. From the viewpoint of the effect, it is preferably 0.5 mass % or more, more preferably 1 mass % or more, and still more preferably 2 mass % or more or 3 mass % or more. The upper limit is not particularly limited, but is, for example, 40 mass % or less, 30 mass % or less, or 20 mass %, preferably less than twice the amount of (A) component content when the non-volatile content in the resin composition is 100 mass % .

<(D) Radical Generator> The resin composition of the present invention contains (D) a radical generator. As the component (D), a thermal radical generator is preferably used. Thermal free radical generators generally generate free radicals by imparting thermal energy.

Examples of the thermal radical generator include dialkyl groups such as di-tert-butyl peroxide, dicumyl peroxide, and tert-butyl peroxy-2-ethylhexanoate. Peroxides; diacyl peroxides such as lauryl peroxide, benzyl peroxide, benzyl tolyl peroxide, tolyl peroxide, etc.; peracetic acid No. Peroxyesters of tributyl ester, 3-butyl peroxyoctanoate, 3-butyl peroxybenzoate, etc.; ketone peroxides; peroxycarbonates; 1,1-bis(tert-amyl peroxide) 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(isobutyronitrile) Azonitrile compounds such as '-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc., 2,2' -Azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} and other azoamide compounds; 2,2'-azobis Azoamidine compounds such as (2-amidinopropane) dihydrochloride and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride; 2,2' - Azobis(2,4,4-trimethylpentane), 4,4'-azobis(4-cyanovaleric acid) and other azobis compounds; 2,2'-azobis( Azo compounds having an oxime skeleton such as 2-methylpropionamide oxime), azo compounds such as 2,2'-azobis(isobutyric acid) dimethyl ester, and the like. A thermal radical generator may be used individually by 1 type, and may be used in combination of 2 or more types in arbitrary ratios. When the azo compound is decomposed, since nitrogen is usually generated, voids tend to be easily generated in the cured product of the resin composition, but in the present invention, it can be suitably used. As the thermal radical generator, among the above-exemplified peroxide-based thermal radical generators and azo compound-based thermal radical generators, from the viewpoint of suppressing generation of voids, peroxide-based thermal radical generators are more preferably used. Producer.

As the thermal radical generator, a medium-temperature active agent is preferable. Specifically, the component (D) is preferably one or more selected from thermal radical generators whose 10-hour half-life temperature T10 (°C) is in the range of 50°C to 110°C, more preferably 10-hour half-life temperature T10 (°C) is one or more thermal radical generators in the range of 50°C to 100°C, and from the viewpoint of obtaining a cured product with less warpage, it is more preferably selected from a 10-hour half-life temperature T10 (°C) of 50°C One or more thermal radical generators in the range of ~80℃. Examples of such commercially available products include "LUPEROX 531M80" manufactured by ARKEMA FUJI, "PERHEXYL (registered trademark) O" manufactured by NOF Corporation, and "MAIB" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

Moreover, it is preferable that the difference ΔT (°C) between the mold temperature Tc (° C.) at the time of compression molding and the 10-hour half-life temperature T10 (° C.) of the (D) component is 20° C. or more and 80° C. or less. , more preferably one or more free radical generators in the range of 30°C or higher and 80°C or lower. That is, when determining the mold temperature Tc (°C) used for compression molding, it is preferable to select a thermal radical generator whose difference ΔT (°C) satisfies the above range as the component (D) to be included in the resin composition of the present invention. Thereby, a cured product with less warpage can be obtained.

The content of the component (D) is not limited as long as the intended effect of the invention can be exhibited, but when the nonvolatile content in the resin composition is 100% by mass, it is, for example, 0.02% by mass or more and 5% by mass or less, and 0.03% by mass or more and 4% by mass. % or less, or 0.04 mass % or more and 3 mass % or less. The content of the component (D) is not limited if only the intended effect of the present invention can be achieved, but when the components other than the (E) inorganic filler in the non-volatile components in the resin composition are set to 100% by mass, it is, for example, 0.02% by mass 5 mass % or more, 0.1 mass % or more and 4 mass % or less, or 0.2 mass % or more and 3 mass % or less.

<(E) Inorganic fillers> The resin composition of the present invention contains (E) an inorganic filler. When the resin composition contains the component (E), a cured product with less warpage can be obtained.

The material of the inorganic filler is not particularly limited as long as it is an inorganic compound, for example, silicon oxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite , boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanic acid Magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, the most preferred is silicon oxide. Examples of silicon oxide include amorphous silicon oxide, fused silicon oxide, crystalline silicon oxide, synthetic silicon oxide, hollow silicon oxide, and the like. And as silicon oxide, spherical silicon oxide is preferable. The inorganic filler may be used alone or in combination of two or more. Examples of commercially available silicon oxides include "SO-C2" and "SO-C1" manufactured by ADMATECHS, and "UFP-30" and "UFP-40" manufactured by DENKA.

The average particle size of the inorganic filler is usually 30 μm or less, and from the viewpoint of improving the intended effect of the present invention, preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 18 μm or less. The lower limit of the average particle size may be 1 nm (0.001 μm) or more, 5 nm or more, or 10 nm or more, but from the viewpoint of improving the intended effect of the present invention, it is preferably 1.0 μm or more, more preferably 1.2 μm or more, and still more preferably 1.4 μm above.

The average particle size of the inorganic filler can be based on the Mie scattering theory, and the laser diffraction can be used. Scattering method. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction particle size distribution analyzer, and the median diameter can be measured as an average particle size. As a measurement sample, the thing obtained by measuring 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in an ampoule and dispersing it ultrasonically for 10 minutes can be used. A laser diffraction particle size distribution analyzer was used for the measurement sample, and the wavelength of the light source used was set to blue and red, and the volume-based particle size distribution of the inorganic filler was measured by a flow cell method. Next, the average particle diameter was calculated from the obtained particle diameter distribution as the median diameter. As a laser diffraction particle size distribution measuring apparatus, for example, "LA-960" manufactured by Horiba Seisakusho Co., Ltd., etc. is exemplified.

From the viewpoint of good embedding properties, the inorganic filler is preferably treated with a surface treatment agent, more preferably a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, and a silane-based coupling agent. Coupling agent, alkoxysilane compound, organosilazane compound, acryloyl silane compound, methacryloyl silane compound, titanate coupling agent and other surface treatment agent treatment, and more It is preferably treated with an aminosilane-based coupling agent. The surface treatment agent preferably has a functional group, such as an epoxy group, an amine group or a carboxyl group, which reacts with other components such as resin, and the functional group is more preferably bonded to a terminal group. Examples of commercially available surface treatment agents include silane-based coupling agent "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., silane-based coupling agent "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. (3-mercaptopropyltrimethoxysilane), silane-based coupling agent "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., silane-based coupling agent "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. (N-Phenyl-3-aminopropyltrimethoxysilane), Silane-based coupling agent "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., alkoxylated by Shin-Etsu Chemical Co., Ltd. Silane compound "KBM103" (phenyltrimethoxysilane), silane-based coupling agent "KBM-4803" (glycidoxyoctyltrimethoxysilane; long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., Silane-based coupling agent "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc. Among them, as the surface treatment agent, silane-based coupling agents "KBM573", "KBM4803" and "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd. are preferably used. Furthermore, from the viewpoint of obtaining a cured product with less warpage, a long-chain epoxy-type silane coupling agent is preferable, and a long-chain epoxy-type silane coupling agent which is a long-chain epoxy-type silane coupling agent having an epoxy group is particularly preferable.

The degree of surface treatment by the surface treatment agent is based on the viewpoint of good embeddability, etc., relative to 100 parts by mass of the (E) component, preferably 0.2 to 5 parts by mass of the surface treatment agent, more preferably 0.2 parts by mass Part to 4 parts by mass of surface treatment, and preferably 0.3 parts by mass to 3 parts by mass of surface treatment.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and still more preferably 0.2 mg/m ² or more, from the viewpoint of good embeddability. . On the other hand, from the viewpoint of suppressing the increase of the melt viscosity of the resin varnish and the melt viscosity of the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg/m ² or less .

The carbon content per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface-treating agent, and ultrasonic cleaning was performed at 25° C. for 5 minutes. After removing the supernatant and drying the non-volatile components, the carbon content per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, for example, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

The specific surface area of the component (E) is preferably 0.3 m ² /g or more, more preferably 0.5 m ² /g or more, and particularly preferably 0.7 m ² /g or more. The upper limit is not particularly limited, but is preferably not more than 60 m ² /g, not more than 50 m ² /g, or not more than 40 m ² /g. The specific surface area can be obtained by adsorbing nitrogen gas on the surface of the sample using a BET automatic specific surface area measuring device (“Macsorb HM-1210” from Mauntech) according to the BET method, and calculating the specific surface area using the BET multipoint method.

The content of the component (E) is preferably high filling in the resin composition, and when the nonvolatile content in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product with less warpage, etc., preferably 70 mass % or more, more preferably 71 mass % or more, still more preferably 72 mass % or more, and the upper limit depends on the content of other components, but may be, for example, 95 mass % or less, 93 mass % or less, or 90 mass % or less.

<(F) Hardening accelerator> The resin composition may contain (F) a hardening accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators, and preferably phosphorus-based curing accelerators and imidazole-based curing accelerators An accelerator, more preferably an imidazole-based hardening accelerator. A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, (4-methylphosphonium decanoate) Phenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium decanoate .

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylamino) methyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4 ,0)-undecene. As a commercial item of an amine type hardening accelerator, "DMP-30" by Fujifilm Wako Pure Chemical Industries, Ltd. can be used, for example.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, Methylguanidine, 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-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1 , 1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., preferably Dicyandiamide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene. As a commercial item of a guanidine-based hardening accelerator, one selected from pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5, One or more kinds of 7-triazabicyclo[4.4.0]dec-5-ene.

Examples of imidazole-based hardening accelerators include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate acid salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'- Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1') ]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2 - Phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro- 1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. The imidazole compound and the adduct of the imidazole compound and the epoxy resin are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

Commercially available products can also be used as imidazole-based hardening accelerators. Examples include imidazole compounds "1B2PZ" and "2E4MZ" manufactured by Shikoku Chemical Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, and "2MA- OK-PW" and so on.

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, and organocopper such as copper(II) acetylacetonate. Complexes, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate compounds, organic manganese complexes such as manganese (II) acetylacetonate, etc. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When the resin composition contains the component (F), the content of the component (F) is, for example, 0.01 mass % or more and 5 mass % or less, and 0.05 mass % or more and 4 mass %, when the nonvolatile matter in the resin composition is 100 mass %. % or less, 0.08 mass % or more and 3 mass % or less. The content of the component (F) is, for example, 0.05 mass % or more and 10 mass % or less, and 0.1 mass % or more and 5 mass %, when the components other than the (E) inorganic filler in the nonvolatile components in the resin composition are set at 100 mass %. % or less, or 0.2 mass % or more and 3 mass % or less.

<(G) Compounds having a radically polymerizable unsaturated group (excluding compounds having a polyalkylene oxide structure)> The resin composition of the present invention preferably further contains (G) a compound having a radically polymerizable unsaturated group (except for a compound having a polyalkylene oxide structure). As (G) component, 2 or more types can be used. By making the resin composition contain the (G) component in addition to the (B) component, the radical polymerization reaction is promoted or competitively carried out, and by making the (G) component play a part of the function of the (B) component, it is considered possible. Those who improve the expected effect of the present invention.

The radically polymerizable unsaturated group which the component (G) has is exemplified by a group containing a carbon-carbon double bond. Specific examples include vinyl, allyl, 1-butenyl, 2-butenyl, acryl, methacryloyl, fumaric, maleic, vinylphenyl, benzene One or more of vinyl group, cinnamonyl group and maleimide group. The component (G) may contain two or more radically polymerizable unsaturated groups in one molecule. The radically polymerizable unsaturated group possessed by the component (G) preferably contains at least one selected from the group consisting of a methacryloyl group and an acryl group from the viewpoint of improving the reactivity, and more preferably contains from the viewpoint of controlling the reactivity Methacryloyl.

Specific examples of the component (G) include those selected from the group consisting of vinyl, allyl, 1-butenyl, 2-butenyl, acryl, methacryloyl, fumarate, maleinyl, A compound of one or more radically polymerizable unsaturated groups of vinylphenyl group, styryl group, cinnamyl group and maleimide group. From the viewpoint of obtaining a cured product excellent in heat resistance, the component (G) preferably contains one or more monovalent or divalent aromatic hydrocarbon groups in the molecule, and preferably contains two or more monovalent or divalent aromatic groups in the molecule family of hydrocarbons. As a monovalent or divalent aromatic hydrocarbon group, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenylene group, a 1-naphthylene group, a 2-naphthylene group, and the like are exemplified. Two or more monovalent or divalent aromatic hydrocarbon groups may be bonded to each other directly or via a linking group, and by this bonding, for example, a bisphenol structure, preferably a bisphenol A structure, can be formed.

The (G) component is more preferably a compound containing a group having reactivity with the (A) component in the molecule. Thereby, a cross-linked structure can be formed, and the warpage of the hardened body can be further reduced. As a group which has reactivity with (A) component, an epoxy group, -OH, _-NH2 , and -COOH are mentioned. In addition, when component (G) is a compound having an epoxy group in the molecule, as long as it is a compound having a radically polymerizable unsaturated group (excluding compounds having a polyalkylene oxide structure), it is classified as component (G) . As the component (G), one or more compounds containing a group reactive with the component (A) in the molecule and one or more compounds containing no group reactive with the component (A) in the molecule may be used in combination.

Moreover, (G) component may be the compound which has an alkylene oxide structure in a molecule|numerator. The alkylene oxide structure possessed by the component (G) is, for example, represented by the formula (3): -(R ^C O) _n -, wherein, in the formula (3), n is an integer of 1, and R ^C may have a substituent The carbon number of 1 to 6 alkyl groups.

The content of the component (G) may be arbitrary as long as the radical polymerization of the component (B) is not excessively impaired, but the components other than the (E) inorganic filler in the non-volatile components in the resin composition are set to 100. The mass % is, for example, 20 mass % or less, 19.5 mass % or less, or 19 mass % or less. From the viewpoint of improving the expected effect of the present invention, the lower limit is preferably 1 mass % or more, more preferably 1.3 mass % or more, still more preferably 1.5 mass % or more, and particularly preferably 1.6 mass % or more.

<(H) Optional additives> In one embodiment, the resin composition may further contain (H) other additives as needed. Examples of the other additives include hardeners other than (C) component, thermoplastic resins, organic fillers, organic copper compounds, and organic zinc. Compounds and organometallic compounds such as organic cobalt compounds, and resin additives and solvents such as tackifiers, defoaming agents, leveling agents, adhesion imparting agents and colorants. The content of the component (H) may be arbitrary as long as the intended effect of the present invention is not unduly impaired, but when the nonvolatile content in the resin composition is 100% by mass, it is, for example, 0.1% by mass or more and 0.3% by mass or more Or 0.5 mass % or more, and may be, for example, 15 mass % or less, 13 mass % or less, or 10 mass % or less.

Examples of curing agents other than the component (C) include active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, carbodiimide-based curing agents, benzoxazine-based curing agents, and amine-based curing agents. As a hardening agent, 1 or more types of hardening|curing agent of a guanidine type|system|group hardener, and a cyanate type|system|group hardener, a commercial item can be used, for example. From the viewpoint of obtaining a resin composition layer (compression-molded body) excellent in film releasability, as the curing agent other than the component (C), those selected from active ester-based curing agents, phenol-based curing agents, and naphthol-based curing agents are preferably used. 1 or more types of curing agents in the group consisting of a carbodiimide-based curing agent, a benzoxazine-based curing agent, and a cyanate-based curing agent. One or more curing agents selected from amine-based curing agents (eg, "KAYAHARD A-A" manufactured by Nippon Kayaku Co., Ltd.) and guanidine-based curing accelerators (eg, dicyanodiamide ("DICY7" manufactured by Mitsubishi Chemical Corporation)) can be used for curing agent, as long as it does not unduly impair the intended effect of the present invention.

Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyimide resins, polyetherimide resins, polysiloxane resins, and polyetherimide resins. , polyphenylene ether resin, polyether ether ketone resin, polyester resin, etc. The thermoplastic resin preferably has a reactive functional group, whereby a crosslinked structure composed of the (A) component can be incorporated. In addition, the reactive functional group may express reactivity by heating or light irradiation. The content of the thermoplastic resin can be arbitrary as long as it does not unduly impair the desired effect of the present invention, but when the nonvolatile content in the resin composition is 100% by mass, it is, for example, 0.1% by mass or more, 0.2% by mass or more, or 0.3 mass % or more may be 5 mass % or less, 3 mass % or less, or 1 mass % or less from the viewpoint of improving the crosslinking density.

As the organic filler, any organic filler that can be used when forming an insulating layer of a printed wiring board is preferably used, such as rubber particles, polyamide fine particles, silicon oxide particles, and the like. As the rubber particles, commercially available products can be used, for example, "EXL2655" manufactured by Dow Chemical Japan, "AC3401N", "AC3816N" manufactured by AICA Industries, and the like. The content of the organic filler may be arbitrary as long as it does not unduly impair the intended effect of the present invention, but when the nonvolatile content in the resin composition is 100% by mass, it may be, for example, 0.1% by mass or more and 0.3% by mass or more Or 0.5 mass % or more, for example, 10 mass % or less, 7 mass % or less, or 5 mass % or less.

When the resin composition contains a solvent, the amount of the solvent is preferably small. When the nonvolatile content of the resin composition is 100% by mass, the content of the solvent is more preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0% by mass (excluding). In addition, in order to reduce the amount of the solvent, it is preferable to use a liquid component as at least one component selected from the group consisting of (A) component, (C) component, (D) component, (F) component and (G) component.

<Characteristics of resin composition> (elastic modulus of warpage) The resin composition of the present invention has less warpage of the cured product obtained by curing at 150° C. for 60 minutes. Specifically, as evaluated in the Example column, in a laminate including a silicon wafer and a cured product formed on the above-mentioned silicon wafer, the measured warpage amount is, for example, less than 2300 μm, more preferably less than 2000 μm, and More preferably, it is less than 1500 μm. In addition, the resin composition of the present invention has a large elastic modulus of the cured product obtained by curing at 150° C. for 60 minutes. Specifically, as evaluated in the column of Examples, the elastic modulus of the cured product at 25° C. is, for example, 7 GPa or more, and more preferably 9 GPa or more. Therefore, the resin composition of this invention can obtain the hardened|cured material of the 1st fold disintegration.

(Inorganic Material Adhesion and Film Material Releasability) The resin composition of the present invention is excellent in the adhesion to inorganic materials of the cured product obtained by curing at 150° C. for 60 minutes. Specifically, as evaluated in the Example column, in the laminate including the copper foil and the cured product formed on the copper foil, the measured adhesion strength (copper foil peeling strength) is, for example, 100 kgf/cm ² or more . Moreover, the resin composition layer (compression molding) obtained by hardening the resin composition of this invention for 10 minutes at 130 degreeC is excellent in the releasability of the film material. Specifically, as evaluated in the Example column, after the resin composition layer (compression-molded body) was compression-molded, the mold was opened with a normal driving force, and it was observed whether the resin composition layer was peeled off from the release film and remained in the mold. on silicon wafers. Therefore, the resin composition of this invention can obtain the resin composition layer (compression molding) and hardened|cured material which the 2nd fold was digested.

As described above, the resin composition of the present invention can obtain a cured product with small warpage, high elastic modulus, and excellent adhesion to inorganic materials, and can exhibit the effect of excellent releasability to film materials. Although the reasons for exhibiting these effects are not entirely clear, the resin composition of the present invention contains (A)-(E) components, and the weight ratio of (B) component to (C) component is within a specific range, It was unexpectedly found that the above-mentioned 1st and 2nd buckling tended to be eliminated. Furthermore, since the resin composition of the present invention has a high elastic modulus of its cured product, specifically, its elastic modulus at 25° C. is large, it is possible to improve the performance of a sealed body including a semiconductor chip and a cured product embedded with a semiconductor chip, for example. . In addition, since the resin composition of the present invention has excellent adhesion to the inorganic material of the cured product, it has high reliability as a sealing material for sealing a semiconductor wafer, for example. Furthermore, since the resin composition of the present invention has excellent releasability of the film material of the resin composition layer (compression-molded body), it can be easily removed from the mold after compression-molding.

The resin composition of the present invention can obtain an insulating layer formed of a cured product with small warpage, excellent adhesion to inorganic materials, and high elastic modulus. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board), and can be more preferably used as a resin composition for forming a printed wiring board Resin composition for interlayer insulating layer between boards (resin composition for forming interlayer insulating layer between printed wiring boards). Furthermore, since the resin composition of the present invention can provide an insulating layer with little warpage, excellent adhesion to inorganic materials, and high elastic modulus, it can also be suitably used when a printed wiring board is a component built-in circuit board. Furthermore, since the resin composition of the present invention can provide an insulating layer formed of a cured product with small warpage, excellent adhesion to inorganic materials, and high elastic modulus, it can be suitably used as a resin for forming a solder resist layer. Composition (resin composition for forming a solder resist layer of a printed wiring board). Moreover, since the resin composition of the present invention can provide an insulating layer formed of a cured product with little warpage, excellent adhesion to inorganic materials, and a large elastic modulus, it can be preferably used as a package for sealing semiconductor chips. The resin composition of the sealing layer of the semiconductor chip (the resin composition for forming the sealing layer of the semiconductor chip package). In addition, the resin composition of the present invention can be preferably used as a resin composition for forming a rewiring-forming layer of a semiconductor chip package (resin composition for a rewiring-forming layer for semiconductor chip packaging).

The semiconductor chip package including the rewiring formation layer can be manufactured, for example, by a manufacturing method described later. Also, when manufacturing a semiconductor chip package including an encapsulation layer, a rewiring layer may be further formed on the encapsulation layer.

<Manufacturing method of resin composition layer> The manufacturing method of the resin composition of this invention is not specifically limited, For example, the preparation component is mixed with a solvent as needed, and the method of dispersing using a rotary mixer etc. is mentioned, for example.

The resin composition can be obtained as a resin varnish by, for example, containing a solvent. In one embodiment, the amount of the solvent is preferably small, and when the nonvolatile content of the resin composition is 100% by mass, the amount of the solvent is more preferably 0.5% by mass or less, and more preferably 0.1% by mass or less.

<Physical properties and uses of resin composition layer or cured product of resin composition> (Warpage and Modulus of Elasticity) The cured product obtained by thermally curing the resin composition of the present invention generally has less warpage. For example, in a cured product with a thickness of 100 μm of the resin composition, in a laminate including a silicon wafer and a cured product formed on the above-mentioned silicon wafer, the measured warpage amount is, for example, less than 2300 μm, more preferably less than 2000 μm , and better still less than 1500 μm. In addition, the cured product obtained by thermally curing the resin composition of the present invention generally has a large elastic modulus. For example, the cured product of the resin composition generally has an elastic modulus at 25° C. of 7 GPa or more, preferably 9 GPa or more. Therefore, in the hardened|cured material of the resin composition of this invention, the 1st fold is normally eliminated.

(Inorganic material adhesion) The cured product obtained by thermosetting the resin composition of the present invention is usually excellent in inorganic material adhesion. For example, in a cured product with a thickness of 300 μm of the resin composition, in a laminate including a copper foil and a cured product formed on the copper foil, the measured adhesion strength (copper foil peel strength) is usually 100 kgf/cm ² or more. In addition, since the resin composition layer (compression-molded body) of the resin composition of the present invention is excellent in releasability as the aforementioned film material, the cured product obtained by thermosetting the resin composition of the present invention is usually easy to self-compression molding. The one used to remove the mold. Therefore, in the cured product of the present invention, the second folding punch is usually dissolved.

The cured product of the resin composition of the present invention has small warpage, excellent adhesion to inorganic materials, and high elastic modulus. Therefore, the hardened|cured material of the resin composition of this invention can be used suitably as an insulating layer of a printed wiring board, and can be used more suitably as an interlayer insulating layer of a printed wiring board. In addition, the cured product of the resin composition of the present invention provides an insulating layer with little warpage, excellent adhesion to inorganic materials, and a large elastic modulus, so that it can be suitably used even when the printed wiring board is a component built-in circuit board. Furthermore, the cured product of the resin composition of the present invention can provide an insulating layer formed of a cured product with little warpage, excellent adhesion to inorganic materials, and a high elastic modulus, so it can be used more appropriately as a solder resist layer. In addition, the cured product of the resin composition of the present invention provides an insulating layer with little warpage, excellent adhesion to inorganic materials, and a large elastic modulus, so it can be suitably used as a sealing layer for sealing semiconductor chips for semiconductor chip packaging. And the hardened|cured material of the resin composition of this invention can be used suitably as a rewiring formation layer (insulation layer) for forming the rewiring layer of a semiconductor chip package.

[resin sheet] The resin paste of the present invention includes the above-mentioned resin composition. The resin paste of the present invention usually contains only the above-mentioned resin composition. The viscosity of the resin paste at 25°C is preferably in the range of 20Pa･s~1000Pa･s. In order to suppress the generation of voids, the heating loss of the resin paste is preferably 5% or less.

[Resin composition molding] The resin composition of the present invention can be formed into a resin composition molded body by compression molding or the like. Moreover, the shape of the resin composition molded body is not limited to a sheet shape, and the resin composition can be processed into any shape. Furthermore, the resin composition of the present invention can also be formed into powder, granular, or flake-shaped resin composition moldings (also referred to as resin powder, resin particles, resin pellets).

[resin sheet] The resin sheet of the present invention includes a support and a resin composition layer containing the resin composition of the present invention provided on the support.

The thickness of the resin composition layer of the resin sheet is usually 600 μm or less, preferably 500 μm or less, and may be 400 μm or less or 300 μm or less from the viewpoint of thinning the printed wiring board. The thickness can be even smaller. The lower limit of the thickness of the resin composition layer is not particularly limited, but is usually 1 μm or more, 10 μm or more, 50 μm or more, or the like.

As the support, for example, a film made of a plastic material, a metal foil, or a release paper, preferably a film or a metal foil made of a plastic material.

When a film made of a plastic material is used as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PET"), Polyester such as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC) , polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using a metal foil as a support body, as a metal foil, a copper foil, an aluminum foil, etc. are mentioned, for example, Preferably it is a copper foil. As the copper foil, a foil made of a single metal of copper, or an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

The support body may be subjected to matte treatment, corona treatment, and antistatic treatment on the surface bonded to the resin composition layer.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined to the resin composition layer can also be used. Examples of the release agent used in the release layer as the support with the release layer include one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Release agent. Commercially available products can be used as a support for the release agent, for example, "SK-1" and "AL-5" manufactured by LINTEC Corporation of a PET film having a release layer containing a glycolic acid resin-based release agent as a main component ", "AL-7", "LUMIRROR T60" manufactured by Toray Corporation, "PUREX" manufactured by Teijin Corporation, "UNIPEEL" manufactured by UNITIKA Corporation, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, when using the support body with a mold release layer, it is preferable that the whole thickness of the support body with a mold release layer is the said range.

In one embodiment, the resin sheet may be further layered as necessary. As this other layer, for example, the protective film according to the support provided on the surface (that is, the surface opposite to the support) of the resin composition layer which is not joined to the support is exemplified. The thickness of the protective film is not particularly limited, but may be, for example, 1 μm˜40 μm. By laminating a protective film, adhesion of dirt, etc. to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and drying to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbitol Acetates such as alcohol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide (DMAc) and amide-based solvents such as N-methylpyrrolidone and the like. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types. In one embodiment, the amount of the organic solvent is preferably small (for example, when the nonvolatile content in the resin composition is 100% by mass, it is 0.5% by mass or less, 0.1% by mass or less, and 0.01% by mass or less), particularly preferably to be solvent-free.

Drying can be carried out by conventional methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it varies with the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, a resin composition can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes. layer.

The resin sheet can be wound into a roll shape and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

The resin sheet of the present invention can provide an insulating layer formed of a cured product with little warpage, excellent adhesion to inorganic materials, and high elastic modulus. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer of a printed wiring board (a resin sheet for forming an insulating layer of a printed wiring board), and more suitably as a resin sheet for forming an interlayer insulating layer of a printed wiring board Resin sheet (resin sheet for interlayer insulating layer of printed wiring board) is used. In addition, the resin sheet of the present invention can be suitably used as a resin sheet for forming a solder resist layer of a printed wiring board (resin sheet for forming a solder resist layer of a printed wiring board). Furthermore, since the resin sheet of the present invention can provide an insulating layer formed of a cured product with little warpage, excellent adhesion to inorganic materials, and a large elastic modulus, it can be suitably used as a semiconductor chip for forming a sealed semiconductor chip package. The resin composition of the sealing layer (resin sheet for forming the sealing layer of the semiconductor chip package) is used. In addition, the resin sheet of the present invention can be suitably used as a resin sheet for forming a rewiring-forming layer (insulating layer) of a semiconductor chip package (resin sheet for forming a rewiring-forming layer for a semiconductor chip package).

＜Printed wiring board＞ The printed wiring board of the present invention includes an insulating layer formed of a cured product containing the resin composition of the present invention. The printed wiring board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2). (1) A step of forming a resin composition layer containing the resin composition using the resin composition of the present invention on a substrate. (2) A step of thermosetting the resin composition layer to form an insulating layer. For example, the method for producing a printed wiring board of the present invention includes forming a resin composition layer containing the resin composition of the present invention or a resin composition layer containing the resin paste of the present invention by compression molding on a circuit board. step, and the step of hardening the aforementioned resin composition layer.

In step (1), a substrate is prepared. Examples of the substrate include substrates such as glass epoxy substrates, metal substrates (stainless steel or cold rolled steel sheet (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. In addition, the base material can also have a metal layer such as copper foil on the surface as a part of the base material. For example, it can be used for a substrate having a peelable first metal layer and a second metal layer on both surfaces. When these base materials are used, a conductor layer, which is a wiring layer that can function as a circuit wiring, is usually formed on the surface of the second metal layer on the opposite side to the first metal layer. As an example of the base material having these metal layers, for example, the ultra-thin copper foil "Micro Thin" of copper foil with a carrier manufactured by Mitsui Metal Mining Co., Ltd. is used.

In addition, a conductor layer may be formed on the surface of one or both of the substrates. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be appropriately referred to as "the base material with a wiring layer". Examples of the conductor material contained in the conductor layer include, for example, a material selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium A material of one or more metals. As the conductor material, a single metal or an alloy may be used. Examples of the alloy include alloys of two or more metals selected from the above-mentioned group (eg, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal, and nickel as an alloy are preferred from the viewpoints of wide availability, cost, and ease of patterning of conductor formation. ･Alloys of chromium alloys, copper-nickel alloys and copper-titanium alloys. Among them, more preferred are single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys, and particularly preferred are single metals of copper.

The conductor layer may be patterned, for example, in order to function as a wiring layer. In this case, the line (circuit width)/space (interval between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, Still more preferably, it is 5/5 μm or less, still more preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The pitch need not necessarily be the same over the entire conductor layer. The minimum pitch of the conductor layers may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductor layer depends on the design of the printed wiring board, but is preferably 3μm~35μm, more preferably 5μm~30μm, still more preferably 10μm~20μm, and particularly preferably 15μm~20μm.

The conductor layer can be formed by a method including the following steps: a step of laminating a dry film (photosensitive resist film) on a substrate; using a photomask to expose and develop the dry film under specific conditions to form a pattern to obtain A step of forming a patterned dry film; a step of forming a conductor layer by a plating method such as electrolytic plating using the developed patterned dry film as a plating mask; and a step of peeling off the patterned dry film. As a dry film, the photosensitive dry film which consists of a photoresist composition can be used, for example, the dry film which consists of resins, such as a novolak resin and an acrylic resin, can be used. The lamination conditions of the base material and the dry film are the same as the lamination conditions of the base material and the resin sheet described later. The peeling of the dry film can be performed using an alkaline peeling solution such as a sodium hydroxide solution.

After preparing the base material, a resin composition layer is formed on the base material. When the conductor layer is formed on the surface of the substrate, the resin composition is preferably formed by embedding the conductor layer in the resin composition layer.

The resin composition layer is formed, for example, by laminating a resin sheet and a base material. This lamination can be performed by, for example, bonding the resin sheet to the base material from the side of the support body, and bonding the resin composition layer to the base material. Examples of the member for thermally pressing the resin sheet to the base material (hereinafter sometimes referred to as a "heat-pressing member") include, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll, etc.). Furthermore, it is preferable that the thermocompression member is not pressed directly on the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the base material.

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

After lamination, a smoothing treatment of the laminated resin sheet may be performed under normal pressure (at atmospheric pressure) by, for example, pressurizing the thermocompression member from the side of the support. The pressing conditions of the smoothing treatment can be set to the same conditions as the heat pressing conditions of the above-mentioned laminate. In addition, the lamination and the smoothing process may be continuously performed using a vacuum laminator.

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

After the resin composition layer is formed on the base material, the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions of the resin composition layer vary with the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 220°C, more preferably in the range of 140°C to 200°C) ), the hardening time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermosetting the resin composition layer, a preheating treatment of heating the resin composition layer at a temperature lower than the curing temperature may be performed. For example, before the resin composition layer is thermally hardened, the resin composition layer may be preheated at a temperature of usually 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less). Heating is usually performed for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As above, a printed wiring board having an insulating layer can be produced. Moreover, the manufacturing method of a printed wiring board may further include arbitrary steps. For example, when a printed wiring board is manufactured using a resin sheet, the manufacturing method of the printed wiring board may include a step of peeling off the support of the resin sheet. The support body can be peeled off before the thermal curing of the resin composition layer, and can also be peeled off after the thermal curing of the resin composition layer.

The manufacturing method of a printed wiring board may also include the step of grinding|polishing the surface of the insulating layer after forming an insulating layer, for example. The grinding method is not particularly limited. For example, the surface of the insulating layer can be ground using a flat grinding disc.

The manufacturing method of the printed wiring board may also include, for example, the step (3) of connecting the conductor layers between layers, for example, the step of perforating the insulating layer. Thereby, holes such as through holes, through holes, etc. can be formed in the insulating layer. Examples of methods for forming the through holes include laser irradiation, etching, mechanical drilling, and the like. The size or shape of the through holes can be appropriately determined according to the design of the printed wiring board. In addition, in step (3), the interlayer connection can also be performed by grinding or grinding the insulating layer.

After the perforation is formed, it is preferable to perform a step of removing the smear inside the perforation. This step is sometimes referred to as the desmear step. For example, when the conductor layer is formed on the insulating layer by the plating step, the perforation may also be subjected to wet desmear treatment. In addition, when forming a conductor layer on the insulating layer by, for example, a sputtering step, a dry desmear step such as a plasma treatment step may be performed. Furthermore, the insulating layer can also be roughened by a desmear step.

In addition, the insulating layer may be roughened before the conductor layer is formed on the insulating layer. According to the roughening treatment, the surface of the insulating layer including the through-holes can be generally roughened. As the roughening treatment, either dry or wet roughening treatment can be performed. Plasma treatment etc. are mentioned as an example of a dry roughening process. Another example of the wet roughening treatment includes 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 agent.

After the through holes are formed, a conductor layer can be formed on the insulating layer. By forming a conductor layer at the position where the perforation is formed, the newly formed conductor layer and the conductor layer on the surface of the base material are electrically connected to perform interlayer connection. The formation method of the conductor layer is, for example, a plating method, a sputtering method, a vapor deposition method, or the like, and among them, a plating method is preferable. In a preferred embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. In addition, when the support body in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtraction method. The material of the conductor layer to be formed can be a single metal or an alloy. In addition, the conductor layer may have a single-layer structure, or may have a multi-layer structure including two or more layers made of different kinds of materials.

Here, an example of an embodiment in which the conductor layer is formed on the insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, corresponding to the desired wiring pattern, a mask pattern for exposing a part of the plating seed layer is formed. After forming an electrolytic plating layer by electrolytic plating on the exposed plating seed crystal layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by a process such as etching, and a conductor layer having a desired wiring pattern can be formed. In addition, when forming the conductor layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

The manufacturing method of a printed wiring board may also comprise the step (4) of removing a base material. By removing the base material, a printed wiring board having an insulating layer and a conductor layer embedded in the insulating layer is obtained. This step (4) can be performed, for example, when a substrate having a peelable metal layer is used.

＜Semiconductor Chip Package＞ The semiconductor chip package of the first embodiment of the present invention includes the above-mentioned printed wiring board and a semiconductor chip mounted on the printed wiring board. The semiconductor chip package can be manufactured by bonding a semiconductor chip to a printed wiring board. The manufacturing method of the semiconductor chip package of the present invention may also include forming a resin composition layer containing the resin composition of the present invention or a resin composition layer containing the resin paste of the present invention by compression molding on a semiconductor chip. step, and the step of hardening the resin composition layer.

The bonding conditions of the printed wiring board and the semiconductor chip can be any conditions that can connect the terminal electrodes of the semiconductor chip and the circuit wiring conductors of the printed wiring board. For example, conditions used in flip chip mounting of semiconductor chips can be employed. And, for example, a semiconductor wafer and a printed wiring board can be joined via an insulating adhesive.

As an example of the bonding method, a method of pressing a semiconductor wafer to a printed wiring board is exemplified. As a pressing condition, the pressing temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the pressing time is usually in the range of 1 second to 60 seconds. range (preferably 5 seconds to 30 seconds).

Another example of the bonding method is a method of bonding a semiconductor chip by reflowing to a printed wiring board. Reflow conditions can be set in the range of 120°C to 300°C.

After the semiconductor chip is bonded to the printed wiring board, the semiconductor chip can also be filled with a molded underfill material. The above-mentioned resin composition and the above-mentioned resin sheet can also be used as the mold underfill.

The semiconductor chip package of the second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition sealing the semiconductor chip. Such a semiconductor chip package generally functions as a sealing layer by a cured product of a resin composition. For example, the method for manufacturing a semiconductor chip package of the present invention may also include forming a resin composition layer containing the resin composition of the present invention or a resin composition containing the resin paste of the present invention by compression molding on a semiconductor chip. The step of layering, and the step of hardening the resin composition layer.

The manufacturing methods of these semiconductor chip packages include: (A) the step of laminating the temporary fixing film on the substrate, (B) the step of temporarily fixing the semiconductor chip on the temporary fixing film, (C) the step of forming a sealing layer on the semiconductor wafer, (D) the step of peeling the base material and the temporary fixing film from the semiconductor wafer, (E) a step of forming a rewiring formation layer as an insulating layer on the surface of the peeled base material and the temporary fixing film of the semiconductor wafer, (F) a step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and (G) A step of forming a solder resist layer on the rewiring layer. In addition, the manufacturing method of the aforementioned semiconductor chip package may also include: (H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and singulated.

(step (A)) The step (A) is a step of temporarily fixing the film on the base material lamination. The lamination conditions of the base material and the temporary fixing film may be the same as the lamination conditions of the base material and the resin sheet in the manufacturing method of the printed wiring board.

As substrates, for example, silicon wafers; glass wafers; glass substrates; metal substrates of copper, titanium, stainless steel, cold rolled steel plate (SPCC), etc.; Thermally cured substrates; substrates made of bismaleimide triazine resins such as BT resins; etc.

The temporary fixing film can be peeled off from the semiconductor wafer, and any material that can temporarily fix the semiconductor wafer can be used. Commercially available products include "RIVA ALPHA" manufactured by Nitto Denko Corporation.

(step (B)) Step (B) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. Temporary fixing of the semiconductor wafer can be performed, for example, using a flip chip bonder, a wafer bonder or the like. The layout of the semiconductor chip arrangement and the number of arrangements can be appropriately set according to the shape and size of the temporary fixing film, the number of production of the intended semiconductor chip package, and the like. For example, semiconductor wafers are arranged in a matrix of plural rows and plural rows, and are temporarily fixed.

(Step (C)) Step (C) is a step of forming a sealing layer on the semiconductor wafer. The sealing layer is formed of a cured product of the above-mentioned resin composition. The sealing layer is usually formed by a method including a step of forming a resin composition layer on a semiconductor wafer and a step of hardening the thermosetting resin composition layer to form a sealing layer.

The formation of the resin composition layer is preferably performed by a compression molding method. By the compression molding method, a semiconductor wafer and a resin composition are usually arranged in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer covering the semiconductor wafer.

The specific operation of the compression molding method is as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. And the resin composition is apply|coated to the semiconductor wafer temporarily fixed on the temporary fixing film as mentioned above. The semiconductor wafer coated with the resin composition is mounted on the lower mold together with the base material and the temporary fixing film. Then, compression molding is performed by applying heat and pressure to the resin composition by clamping the upper mold and the lower mold.

In addition, the specific operation of the compression molding method may be as follows, for example. As a mold for compression molding, an upper mold and a lower mold are prepared. The resin composition is placed on the lower mold. Then, the semiconductor wafer is mounted on the upper mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are clamped so that the resin composition placed on the lower mold is in contact with the semiconductor wafer mounted on the upper mold, and compression molding is performed by applying heat and pressure. The general compression molding method is to set a release film on the surface of the mold. Therefore, the resin composition is formed in a state of being in contact with the release film. The resin composition containing the components (A) to (E) in combination as described above also has excellent releasability of the release film, so that the self-molded resin composition layer or the mold release of the cured product can be smoothly performed.

The molding conditions vary depending on the composition of the resin composition, and appropriate conditions are adopted to achieve good sealing. For example, the mold temperature (metal mold temperature Tc) 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 Below 150℃. Further, the pressure applied during molding is preferably 1 MPa or more, more preferably 2 MPa or more, particularly preferably 3 MPa or more, preferably 50 MPa or less, more preferably 30 MPa or less, and still more preferably 20 MPa or less. The hardening time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, and particularly preferably 20 minutes or less. Usually, after forming the resin composition layer, the mold is removed. The removal of the mold may be performed before the resin composition layer is thermally hardened, or may be performed after the thermal hardening.

The resin composition layer can be formed by laminating a resin sheet and a semiconductor wafer. For example, the resin composition layer can be formed on the semiconductor wafer by thermally pressing the resin composition layer of the resin sheet and the semiconductor wafer. In the lamination of the resin sheet and the semiconductor wafer, a semiconductor wafer is usually used instead of the base material, and it is carried out in the same manner as the lamination of the resin sheet and the substrate in the manufacturing method of the printed wiring board.

After forming the resin composition layer on the semiconductor wafer, the sealing layer covering the semiconductor wafer is obtained by thermally curing the resin composition layer. Thereby, semiconductor chip packaging using the cured product of the resin composition is performed. The thermosetting conditions of the resin composition layer can be the same as those of the thermosetting conditions of the resin composition layer in the manufacturing method of the printed wiring board. Furthermore, before thermally curing the resin composition layer, a preheating treatment of heating the resin composition layer at a temperature lower than the curing temperature may be performed. The processing conditions of this preheating process can be the same as that of the preheating process of the manufacturing method of a printed wiring board.

(step (D)) Step (D) is a step of peeling off the base material from the semiconductor wafer and temporarily fixing the film. As a peeling method, it is desirable to employ|adopt an appropriate method corresponding to the material of the temporary fixing film. As the peeling method, for example, a method of temporarily fixing a film by heating, foaming or expanding, and peeling is exemplified. Moreover, as a peeling method, the method of irradiating an ultraviolet-ray to a temporary fixing film through a board|substrate, reducing the adhesive force of a temporary fixing film, and peeling is exemplified, for example.

In the method of temporarily fixing the film by heating, foaming or expanding, and peeling off, the heating conditions are usually heating at 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of reducing the adhesive force of the temporary fixing film by irradiating ultraviolet rays, the irradiation amount of the ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

(step (E)) The step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the peeling base material and the temporary fixing film of the semiconductor wafer.

Any material having insulating properties can be used for the material of the rewiring formation layer. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of the easiness of manufacture of the semiconductor chip package. In addition, as this thermosetting resin, the resin composition of this invention can be used.

After the rewiring formation layer is formed, in order to connect the semiconductor wafer and the rewiring layer between layers, a through hole may be formed in the redistribution wiring formation layer.

When the material of the rewiring forming layer is a photosensitive resin, the method of forming a through hole is usually to irradiate the surface of the rewiring forming layer with active energy rays through a mask pattern to photoharden the rewiring forming layer in the irradiated part. Examples of the active energy rays include ultraviolet rays, visible light, electron beams, X-rays, and the like, and ultraviolet rays are 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, for example, a contact exposure method in which a mask pattern is adhered to the rewiring formation layer and exposed, and a non-contact exposure method in which the mask pattern is not adhered to the rewiring formation layer and exposed using parallel rays Wait.

After photocuring the rewiring formation layer, the rewiring formation layer is developed to remove the unexposed portion to form a through hole. The development can be performed either wet development or dry development. As a developing method, for example, a dipping method, a liquid coating method, a spraying method, a brushing method, a scraping method, etc. are exemplified, and from the viewpoint of resolution, the liquid coating method is preferable.

As a method of forming a through hole when the material of the rewiring formation layer is a thermosetting resin, for example, laser irradiation, etching, mechanical drilling, etc. are exemplified. Among them, laser irradiation is preferable. The laser irradiation can be performed using an appropriate laser processing machine of a light source such as a carbon dioxide laser, a UV-YAG laser, and an excimer laser.

The shape of the through hole is not particularly limited, and is generally circular (slightly circular). The diameter of the top of the through hole is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. Here, the diameter of the top of the through hole refers to the diameter of the opening of the through hole on the surface of the rewiring formation layer.

(step (F)) Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring formation layer can be the same as the method of forming the conductor layer on the insulating layer in the manufacturing method of the printed wiring board. Furthermore, by repeating the step (E) and the step (F), the rewiring layer and the rewiring formation layer can be alternately laminated (build-up).

(step (G)) Step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any material having insulating properties can be used. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of the easiness of manufacture of the semiconductor chip package. In addition, as the thermosetting resin, the resin composition of the present invention can be used.

In addition, in the step (G), bump processing for forming bumps may be performed as necessary. Bumping can be performed by methods such as solder balls, solder plating, and the like. In addition, the formation of the through hole in the bump processing can be performed in the same manner as the step (E).

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

<Semiconductor device> The semiconductor device includes a semiconductor chip package. Examples of semiconductor devices are, for example, printed wiring boards, semiconductor chip packages, multi-chip packages, package-on-package, wafer-level packages (eg, fan-out WLP), panel-level packages, system-in-package, and the like. Examples of semiconductor devices include electrical products (such as computers, mobile phones, smart phones, tablet-type devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (such as locomotives, automobiles, and trams). , ships and aircraft, etc.) and other semiconductor devices. [Example]

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In the following description, unless otherwise specified, "part" and "%" indicating the amount mean "part by mass" and "% by mass", respectively. And the operations described below are carried out in a normal temperature and normal pressure environment unless otherwise specified.

[Example 1] <Preparation of Resin Paste A> 10 parts of epoxy resin ("ZX-1059" manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent: 165 g/eq.) as the component (A) was used as (B) 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure (“M-130G” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methacryloyl group equivalent: 628 g/eq.), as ( C) 8 parts of acid anhydride-based hardener ("MH-700" manufactured by Nippon RIKEN Co., Ltd., acid anhydride group equivalent: 163 g/eq.), 8 parts of (D) thermal radical generator ("ARKEMA FUJI Co., Ltd." LUPEROX 531M80", 10-hour half-life temperature T10: 93.0°C, hydrocarbon solution with 80% peroxide content) 0.1 part, imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd.) as component (F) 0.15 part, And inorganic filler A (average particle size: 1.8 μm, specific surface area: 3.6 m ² /g, maximum cut-off diameter: 5 μm, “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., with (N-phenyl- 85 parts of spherical silicon oxide treated with 3-aminopropyltrimethoxysilane), and uniformly dispersed using a mixer. Thereby, a liquid resin composition is prepared. Hereinafter, the liquid resin composition prepared in this way is also referred to as "resin paste A".

<Evaluation of hardened product of resin paste A> Using the obtained resin paste A, a compression-molded body (resin composition layer) or a cured product or a substrate for evaluation including a cured product was obtained, and the obtained compression-molded body (resin composition layer) or cured product or substrate for evaluation was based on the warpage described later. The viewpoints of curvature, modulus of elasticity, adhesion to inorganic substrates, and releasability from film materials were used for evaluation.

[Examples 2 to 6] In Examples 2 to 6, except that 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure ("M-130G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as the component (B) in Example 1 were used , respectively changed to a compound having a methacryloyl group and a polyethylene oxide structure as the component (B) ("M-230G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methacryloyl group equivalent: 1068 g/eq.) 5 parts, a compound having a methacryloyl group and a polyethylene oxide structure as the component (B) ("M-23G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methacryloyl group equivalent: 568 g/eq.) 5 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure as the component (B) ("M-90G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methacryloyl group equivalent: 468 g/eq.) , 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure as component (B) ("M-40G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methacryloyl group equivalent: 276 g/eq.), (B) 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure ("BPE-1300N" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methacryloyl group equivalent: 842 g/eq.).

Resin paste A was prepared in the same manner as in Example 1 except for the above. Then, using the resin paste A, as in Example 1, a compression-molded body (resin composition layer), a cured product, or a substrate for evaluation including the cured product was obtained, and these were evaluated in the same manner as in Example 1.

[Example 7] In Example 6, 85 parts of inorganic filler A as component (E) was changed to inorganic filler B as component (E) (average particle size: 2.6 μm, specific surface area: 1.4 m ² / g, Maximum cut-off diameter: 10 μm, “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd. was treated with 140 parts of (N-phenyl-3-aminopropyltrimethoxysilane-treated spherical alumina).

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Examples 8 and 9] The thermal radical generator (D) component in Example 6 ( 0.1 part of "LUPEROX 531M80" manufactured by ARKEMA FUJI Co., Ltd., a hydrocarbon solution with a peroxide content of 80%), in Example 8, it was changed to a thermal radical generator ("PERBUTYL manufactured by NOF Corporation") as the component (D) (registered trademark) O", 10-hour half-life temperature T10: 69.9°C) 0.1 part, in Example 9, it was changed to a thermal radical generator ("MAIB" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as component (D) "(2,2'-azobis(isobutyric acid) dimethyl ester), 10 hours half-life temperature T10: 67.0°C) 0.1 part.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Example 10] In Example 6, 8 parts of the acid anhydride-based hardener ("MH-700" manufactured by Shin Nippon Chemical Co., Ltd.) as the component (C) was changed to the acid anhydride-based hardener ("HNA" manufactured by Shin Nippon Chemical Co., Ltd.) as the (C) component. -100", acid anhydride group equivalent: 179g/eq.) 8 parts.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Example 11] In Example 6, 8 parts of the acid anhydride-based hardener ("MH-700" manufactured by Shin Nippon Chemical Co., Ltd.) as the component (C) was changed to the acid anhydride-based hardener ("MH-700" manufactured by Shin Nippon RIKEN Co., Ltd.) as the (C) component. -700") 15 parts, and 85 parts of inorganic filler A as component (E) was changed to 100 parts of inorganic filler A as component (E).

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Example 12] 5 parts of the compound having a methacryloyl group and a polyethylene oxide structure ("BPE-1300N" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as the component (B) in Example 6 was changed to the component (B) 10 parts of a compound having a methacryloyl group and a polyethylene oxide structure (“BPE-1300N” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and 85 parts of inorganic filler A as the component (E) was changed to be (E) Inorganic filler A 95 parts.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Example 13] In Example 6, for the component (A), 10 parts of epoxy resin ("ZX-1059" manufactured by Nippon Steel Chemical & Materials Corporation) were changed to epoxy resin ("ZX-1059" manufactured by Nippon Steel Chemical & Materials Corporation). ") 5 parts and epoxy resin ("HP-4032SS" manufactured by DIC Corporation, epoxy equivalent: 143 g/eq.) 5 parts, for component (C), an acid anhydride-based hardener ("MH" manufactured by Nippon Chemical Co., Ltd. -700") 8 parts, changed to 9 parts of acid anhydride-based hardener ("MH-700" manufactured by Nippon Chemical Co., Ltd.), and changed 85 parts of inorganic filler A as component (E) to component (E) Inorganic filler A 90 parts.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Example 14] In Example 6, for the component (A), 10 parts of epoxy resin ("ZX-1059" manufactured by Nippon Steel Chemical & Materials Corporation) were changed to epoxy resin ("ZX-1059" manufactured by Nippon Steel Chemical & Materials Corporation). ") 5 parts and epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy group equivalent: 98 g/eq.) 5 parts, for the component (C), an acid anhydride type hardener ("MH- 700") 8 parts, changed to 11 parts of acid anhydride-based hardener ("MH-700" manufactured by Nippon Chemical Co., Ltd.), and changed 85 parts of inorganic filler A as component (E) to inorganic filler A as component (E) Filler A 95 copies.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Example 15] In Example 6, 85 parts of inorganic filler A as component (E) was changed to inorganic filler C as component (E) (average particle size: 1.8 μm, specific surface area: 3.6 m ² / g, Maximum cut-off diameter: 5 μm, “KBM-4803” manufactured by Shin-Etsu Chemical Co., Ltd. (Spherical silica treated with (glycidyloxyoctyltrimethoxysilane)) 95 parts.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Example 16] In Example 6, 85 parts of inorganic filler A as component (E) was changed to inorganic filler D as component (E) (average particle size: 1.8 μm, specific surface area: 3.6 m ² / g, Maximum cut-off diameter: 5 μm, “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd. (Spherical silica treated with (3-glycidoxypropyltrimethoxysilane)) 85 parts.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Comparative Example 1] In Example 1, 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure ("M-130G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as the component (B) was changed to the component (B'). 5 parts of the compound having the methacryloyl group and the polyethylene oxide structure ("BPE-500" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methacryloyl group equivalent: 402 g/eq.). That is, in Comparative Example 1, (B) component was not used.

Resin paste A was prepared in the same manner as in Example 1 except for the above. Then, using the resin paste A, as in Example 1, a compression-molded body (resin composition layer), a cured product, or a substrate for evaluation including the cured product was obtained, and these were evaluated in the same manner as in Example 1.

[Comparative Example 2] In Example 6, 8 parts of the acid anhydride-based hardener ("MH-700" manufactured by Nippon Chemical Co., Ltd.) as the component (C) was changed to an amine-based hardener ("KAYAHARD" manufactured by Nippon Kayaku Co., Ltd.) as the component (H). A-A") 0.5 parts. That is, in the comparative example 2, (C)component was not used. In addition, in Example 6, 0.15 part of imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd.) as (F) was changed to an imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd.) as component (F) 2E4MZ") 0.2 part, and changed 85 parts of inorganic filler A as component (E) to 60 parts of inorganic filler A as component (E).

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Comparative Example 3] In Comparative Example 2, 0.5 part of the amine-based hardener ("KAYAHARD A-A" manufactured by Nippon Kayaku Co., Ltd.) as the component (H) was changed to dicyanodiamide ("KAYAHARD A-A" manufactured by Mitsubishi Chemical Corporation) as the component (H) DICY7”) 1 serving. That is, the comparative example 3 does not use (C)component similarly to the comparative example 2.

Resin paste A was prepared in the same manner as in Comparative Example 2 except for the above. Then, similarly to Comparative Example 2, using the resin paste A, a compression-molded body (resin composition layer), a cured product, or a substrate for evaluation including the cured product was obtained, and these were subjected to evaluation in the same manner as in Comparative Example 2.

[Comparative Example 4] In Comparative Example 2, 0.5 part of an amine-based hardener (“KAYAHARD A-A” manufactured by Nippon Kayaku Co., Ltd.) as the component (H) was not used. That is, the comparative example 4 does not use (C)component similarly to the comparative example 2.

Resin paste A was prepared in the same manner as in Comparative Example 2 except for the above. Then, similarly to Comparative Example 2, using the resin paste A, a compression-molded body (resin composition layer), a cured product, or a substrate for evaluation including the cured product was obtained, and these were subjected to evaluation in the same manner as in Comparative Example 2.

[Comparative Example 5] In Example 1, 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure (“M-130G” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as the component (B) was not used. That is, in Comparative Example 5, the component (B) was not used. In addition, in Example 1, 85 parts of inorganic filler A as (E) component were changed to 65 parts of inorganic filler A as (E) component.

Resin paste A was prepared in the same manner as in Example 1 except for the above. Then, using the resin paste A, as in Example 1, a compression-molded body (resin composition layer), a cured product, or a substrate for evaluation including the cured product was obtained, and these were evaluated in the same manner as in Example 1.

[Comparative Example 6] In Example 6, 8 parts of the acid anhydride-based hardener ("MH-700" manufactured by Shin Nippon Chemical Co., Ltd.) as the component (C) were changed to the acid anhydride-based hardener ("MH-700" manufactured by Shin Nippon Chemical Co., Ltd.) as the (C) component. -700") 3 servings. Moreover, in Example 6, 85 parts of inorganic filler A as (E) component were changed to 65 parts of inorganic filler A as (E) component.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Comparative Example 7] In Example 6, 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure (“BPE-1300N” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as the component (B) was changed to the component (B) 1 part of a compound having a methacryloyl group and a polyethylene oxide structure ("BPE-1300N" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). In addition, in Example 6, 85 parts of inorganic filler A as (E) component were changed to 70 parts of inorganic filler A as (E) component.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Comparative Example 8] In Example 6, 5 parts of a compound having a methacryloyl group and a polyethylene oxide structure (“BPE-1300N” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as the component (B) was changed to the component (B) 13 parts of a compound having a methacryloyl group and a polyethylene oxide structure ("BPE-1300N" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). In addition, in Example 6, 85 parts of inorganic filler A as (E) component were changed to 110 parts of inorganic filler A as (E) component.

Resin paste A was prepared in the same manner as in Example 6 except for the above. Then, similarly to Example 6, using the resin paste A, a compression-molded body (resin composition layer), a hardened product, or a substrate for evaluation containing the hardened product was obtained, and these were used for evaluation in the same manner as in Example 6.

[Evaluation method] Compression-molded bodies (resin composition layers) or hardened bodies of the resin paste A obtained in the above Examples and Comparative Examples, or evaluation substrates containing the hardened bodies were obtained. From the viewpoint of adhesion and releasability from the film material, evaluation was performed according to the following methods. In addition, Table 1 and Table 2 show each evaluation result.

<Evaluation of peelability from film material> About the resin paste A, the compression molding (resin composition layer) was obtained, and the peelability from a film material was evaluated as follows.

(Preparation of evaluation substrate Bb containing resin composition layer Ba) First, a compression molding apparatus equipped with a mold is prepared. On the mold surface, a release film (a double-sided rough finishing film "Aflex (registered trademark) 50MW" manufactured by AGC Co., Ltd.) was attached. Using the compression molding apparatus, under the conditions of mold temperature Tc: 130° C., pressure: 6 MPa, and curing time: 10 minutes, resin paste A was compression-molded on a 12-inch silicon wafer (substrate). Thereby, in the mold, a substrate for evaluation composed of a silicon wafer and a resin composition layer having a thickness of 150 μm was produced as a compression-molded body of the resin paste A formed on the silicon wafer. The resin composition layer and the evaluation substrate thus produced are hereinafter simply referred to as "resin composition layer Ba" and "evaluation substrate Bb", respectively.

(Evaluation of resin composition layer Ba) Then, after the compression molding is completed, it is confirmed whether the molds are opened (ie, the pair of molds that are connected to each other are separated by the normal driving force set in the compression molding apparatus). Furthermore, when the mold was opened, it was observed whether the resin composition layer Ba was peeled off from the release film and located on the silicon wafer. These confirmation and observation results were evaluated according to the following criteria. "○": Test results, the mold was opened with normal power, and the resin composition layer B was observed to be peeled from the release film and located on the silicon wafer. Therefore, the resin composition layer B was evaluated as the peelability from the film material. Excellent. "X": As a result of the test, the mold could not be opened with the usual power. Or because the resin composition layer B could not be peeled off from the release film, it was observed that (i) the whole of the evaluation substrate Bb was adhered to the release film, or (ii) a part or all of the resin composition layer Ba was self-releasing. Membrane detachment. Therefore, the resin composition layer Ba was evaluated to be inferior in releasability from the film material.

＜Evaluation of warpage＞ The resin composition layer Ba contained in the evaluation substrate Bb prepared during the evaluation of the peelability from the film material was cured to obtain an evaluation substrate including the cured product. Warpage of hardened material.

(Preparation of substrate Cb for evaluation including cured product Ca of resin composition layer Ba) The resin composition layer Ba contained in the substrate Bb for evaluation prepared at the time of evaluating the peelability from the film material was heated at 150° C. for 60 minutes together with the silicon wafer. Thereby, the resin composition layer Ba is thermally cured on the silicon wafer to form a cured product. The cured product of the resin composition layer thus produced and the substrate for evaluation are referred to as "cured product Ca" and "substrate Cb for evaluation" hereinafter, respectively. In addition, in Comparative Examples 2 to 4 and 6, the mold was not opened with the usual driving force due to the evaluation result of the peelability from the film material, so first, the release film was removed from the compression molding apparatus, and then, the release film was removed from the compression molding apparatus on one side. The metal mold|die took out the board|substrate Bb for evaluation in the state in which the release film was attached, and further peeled the release film from the resin composition layer Ba, and obtained the board|substrate Bb for evaluation. Furthermore, in Comparative Examples 2 to 4 and 6, no interfacial peeling was observed between the resin composition layer Ba and the silicon wafer and between the resin composition layer Ba and the release film. Therefore, also in Comparative Examples 2-4 and 6, as mentioned above, the board|substrate Cb for evaluation containing the hardened|cured material Ca of the resin composition layer Ba was obtained.

(Measurement and evaluation of warpage amount) Using a shadow moiré measurement device (Akorometrix, Inc. "Thermoire AXP"), the warpage amount of each evaluation substrate Cb was measured in a room at 25°C. The measurement is performed in accordance with JEITA EDX-7311-24 of the Electronic Information Technology Industry Association standard. Specifically, the virtual plane calculated by the least square method of all the data of the substrate surface of the measurement area is used as the reference plane, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane is obtained as the warpage amount.

The obtained warpage amount was evaluated according to the following criteria. "◎": The warpage amount was less than 1500 μm, and the warpage amount was evaluated as being particularly small. "○": The warpage amount was 1500 μm or more and less than 2000 μm, and the warpage amount was evaluated to be sufficiently small. "△": The warpage amount was 1500 μm or more and less than 2000 μm, and the warpage amount was evaluated as being small. "X": The warpage amount was 2300 μm or more, and it was evaluated that the warpage amount was large.

<Evaluation of Adhesion with Inorganic Materials> The hardened|cured material obtained using the resin paste A was as follows in detail, and the adhesiveness with an inorganic material was evaluated by measuring the adhesive strength with copper foil.

(Preparation of layered body Db including resin composition layer Da of resin paste A) First, a compression molding apparatus equipped with a mold is prepared. Using this compression molding apparatus, under the conditions of mold temperature Tc: 130° C., pressure: 6 MPa, and curing time: 10 minutes, a SUS plate (12 inches) coated with a mold release agent was placed in a thickness of 18 μm. The resin paste A in the state on the glossy side (bright side) of the copper foil was compression-molded. After compression molding, the resin composition layer was peeled off from the SUS plate. Thereby, the laminated body which consists of the 300-micrometer-thick resin composition layer which is the compression-molded body of the resin paste A, and the copper foil provided on the resin composition layer was obtained. The copper foil in the laminate is exposed on its non-glossy surface (matte surface). The resin composition layer and the layered body thus produced are referred to as "resin composition layer Da" and "layered body Db" hereinafter, respectively.

(Preparation of laminated body Eb including cured product Ea of resin composition layer Da) Subsequently, the layered body Db was heated at 150° C. for 60 minutes. Thereby, the resin composition layer Da is directly thermally cured in a state where the copper foil is attached to form a cured product. The cured product and the layered product of the resin composition layer thus produced are referred to as "cured product Ea" and "layered product Eb" hereinafter, respectively.

(Production of Test Piece F) Next, the layered body Eb was cut into a 1 cm square. Thereby, a plurality of test piece materials of 1 cm square and thickness of 318 μm were obtained.

In addition, on the matte surface of the copper foil of each test piece material, a stud pin (φ5.8mm) for attaching the agent is vertically erected. Next, on the surface of the cured product (cured product Ea) of the resin composition layer of the test piece material, the backing plate of the adhesive was superimposed. Thereby, the laminated body provided with the backing plate, the test piece material, and the stud pin was obtained. Next, this laminated body was heated at 150 degreeC for 60 minutes. As a result, the adhesive was cured, the copper foil and the stud pins were fixed, and the laminated body in which the test piece material and the back plate were fixed was obtained. Next, use a dicing knife to cut only the copper foil along the peripheral surface of the stud pin (ϕ5.8 mm) at the junction between the copper foil and the stud pin. The laminate thus obtained is hereinafter referred to as "test piece F".

(Measurement and Evaluation of Adhesion Strength between Cured Product Ea and Inorganic Material) Using a vertical tensile tester "ROMULUS" manufactured by QUAD GROUP, a vertical tensile test was performed on each of the obtained test pieces F at a test speed of 0.1 kg/sec. , to obtain a measurement value representing the peel strength of the copper foil (hereinafter simply referred to as "adhesion strength"). Specifically, the measured value usually represents the adhesion strength between the cured product Ea and the copper foil which is an inorganic material. Five test pieces F were measured, and the average value of the measured values of the bonding strength was calculated. Next, the average value of the measured values of the calculated bonding strength was evaluated according to the following criteria. "○": The average value of the measured values of the adhesive strength was 100 kgf/cm ² or more, and the cured product Ea was evaluated as being excellent in adhesion to the inorganic material. "X": The average value of the measured values of the adhesive strength was less than 100 kgf/cm ² , and the cured product Ea was evaluated to have poor adhesion to the inorganic material.

<Evaluation of elastic modulus> The elastic modulus of the cured product obtained using the resin paste A was evaluated as described in detail below.

(Preparation of Laminated Body Gb Containing Resin Composition Layer Ga of Resin Paste A) Using a compression molding apparatus (mold temperature Tc: 130° C., pressure: 6 MPa, hardening time: 10 minutes), the resin paste A in the state of being placed on the SUS plate whose surface was released from the mold was compression-molded in the mold. . Thereby, the laminated body which consists of the SUS board and the 300-micrometer-thick resin composition layer provided on this SUS board as the compression molding body of the resin paste A was obtained. The resin composition layer and the laminated body thus produced are referred to below as "resin composition layer Ga" and "laminated body Gb", respectively.

(Preparation of cured product H of resin composition layer Ga) Subsequently, the layered body Gb was heated at 150° C. for 60 minutes. As a result, the resin composition layer Ga is thermally cured on the SUS plate to form a cured product. This hardened|cured material was peeled from the SUS board. The cured product of the resin composition layer thus produced is referred to as "cured product H" hereinafter.

(Production of Test Piece I and Measurement and Evaluation of Elastic Modulus at 25°C) Next, three test pieces of the No. 1 form in the shape of a dumbbell in a plan view were cut out from the cured product H. Each test piece thus obtained is hereinafter referred to as "test piece I". Then, with respect to each test piece I, a tensile test was performed in a room at 25°C using a tensile tester "RTC-1250A" manufactured by ORIENT TECH, and the modulus of elasticity (GPa) at 25°C was measured. The measurement system was implemented in accordance with JIS K7127:1999. The average value of the measured values of the elastic modulus at 25° C. of the three test pieces 1 was calculated. Next, the average value of the measured values of the elastic modulus at 25°C calculated according to the following criteria was evaluated. "○": The average value of the measured values of the elastic modulus at 25°C was 9 GPa or more, and the elastic modulus was evaluated as high. "△": The average value of the measured values of the elastic modulus at 25°C was 7 GPa or more and less than 9 GPa, and the elastic modulus was evaluated to be sufficiently high. "X": The average value of the measured values of the elastic modulus at 25°C was less than 7 GPa, and it was evaluated that the elastic modulus was low.

[result] The results of the above Examples and Comparative Examples are shown in Tables 1 and 2 below.

In the following Table 1 and Table 2, the amount of each component represents the non-volatile component conversion amount. In addition, the "resin component" shown in Table 1 and Table 2 means the component other than (E) an inorganic filler among non-volatile components in a resin composition. "Mass ratio [b]:[c]" shows the mass ratio of (B) component with respect to (C) component. "The content ratio of (B) component in a resin component" shows content of (C) component when the resin component in the non-volatile matter in a resin composition is 100 mass %. "Equivalent ratio (c)/(a)" means the sum of the value obtained by dividing the amount (g) of the component (C) by the equivalent weight (g/eq.) of the acid anhydride group contained in the component (C) relative to the amount of the component (A). ) The value of the total equivalent ratio (c)/(a) of the amount (g) of the component divided by the value of the equivalent weight (g/eq.) of the epoxy group which the component (A) has. "Content of (E) component in a resin composition" shows the content of (E) component when content of the non-volatile matter in a resin composition is 100 mass %. "(D) component ΔT" represents the difference (°C) between the mold temperature T (130°C) during compression molding and the 10-hour half-life temperature T10 (°C) of the (D) component.

(式(1)中，E表示自由基聚合性不飽和基之當量(g/eq.)，N表示分子中自由基聚合性不飽和基之數，且為1以上之整數)， (C)酸酐、(D)自由基產生劑及(E)無機填充材，且表示(B)成分相對於(C)成分之質量比的[b]:[c]於0.2:1~1.5:1之範圍內，可獲得翹曲小、彈性率大且對於無機材料之密著性優異之硬化物，可提供對於膜材之剝離性優異之樹脂組成物或樹脂膏。<Review> As can be seen from Tables 1 and 2, based on the comparison between the Examples and the Comparative Examples, in the Examples, the resin compositions contained (A) an epoxy resin and (B) had a radically polymerizable unsaturated group. A compound constructed with an alkylene oxide, and is a compound that satisfies the following formula (1):

(In formula (1), E represents the equivalent of radically polymerizable unsaturated groups (g/eq.), and N represents the number of radically polymerizable unsaturated groups in the molecule, and is an integer of 1 or more), (C) Acid anhydride, (D) radical generator, and (E) inorganic filler, and [b]:[c] representing the mass ratio of (B) component to (C) component is in the range of 0.2:1 to 1.5:1 In this case, a cured product with small warpage, high elastic modulus, and excellent adhesion to inorganic materials can be obtained, and a resin composition or resin paste with excellent peelability to film materials can be provided.

Furthermore, it can be understood that a cured product, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device obtained by using the resin composition or resin paste of the Examples can also be provided.

Claims (26)

A resin composition comprising (A) an epoxy resin, (B) a compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure in the molecule, and a compound satisfying the following formula (1),

(In formula (1), E represents the equivalent of radically polymerizable unsaturated groups (g/eq.), and N represents the number of radically polymerizable unsaturated groups in the molecule, and is an integer of 1 or more), (C) Acid anhydride, (D) radical generator, and (E) inorganic filler, [b]:[c] representing the mass ratio of (B) component to (C) component is in the range of 0.2:1 to 1.5:1 Inside. The resin composition according to claim 1, wherein the polyalkylene oxide structure possessed by the component (B) is represented by the formula: -(R ^B O) _n -, wherein n is an integer of 2 or more, and R and ^B are each independently It is an alkylene group having 1 to 6 carbon atoms which may have a substituent. The resin composition according to claim 2, wherein at least one group ^RB in the plurality of ^RBs comprises an ethylidene group. The resin composition according to claim 1, wherein the radically polymerizable unsaturated group possessed by component (B) is selected from the group consisting of vinyl, allyl, 1-butenyl, 2-butenyl, acrylyl, methyl One or more of acryloyl, fumaric, maleic, vinylphenyl, styryl and cinnamonyl. The resin composition according to claim 4, wherein the radically polymerizable unsaturated group possessed by the component (B) includes at least one selected from the group consisting of a methacryloyl group and an acryl group. The resin composition according to claim 4, wherein the radically polymerizable unsaturated group possessed by the component (B) contains a methacryloyl group. The resin composition according to claim 1, wherein the component (B) comprises at least one compound selected from the group consisting of the compound in which N is 1 in formula (1) and the compound in which N is 2 in formula (1). The resin composition according to claim 7, wherein the compound in which N is 1 in formula (1) has a molecular weight of 150 or more. The resin composition according to claim 7, wherein the compound in which N is 2 in formula (1) has an equivalent weight (g/eq.) of radically polymerizable unsaturated groups of 500 or more. The resin composition of claim 1, wherein the equivalent weight of the radically polymerizable unsaturated group of the component (B) is 4500 g/eq. or less. The resin composition according to claim 1, wherein the content of component (B) is 10% by mass or more and 40% by mass when the nonvolatile components in the resin composition other than (E) the inorganic filler are 100% by mass %the following. The resin composition of claim 1, wherein the sum of the value of the amount (g) of the component (C) divided by the equivalent weight (g/eq.) of the acid anhydride group that the component (C) has is relative to the amount of the component (A) The value of the total equivalent ratio (c)/(a) obtained by dividing the amount (g) by the value of the equivalent weight (g/eq.) of the epoxy group contained in the component (A) is 0.4 or more. The resin composition of claim 1, wherein the component (D) is one or more types of radical generators selected from the group consisting of a 10-hour half-life temperature T10 (°C) in the range of 50°C or more and 110°C or less. The resin composition of claim 1, wherein the content of the component (E) is 70 mass % or more when the non-volatile content in the resin composition is 100 mass %. The resin composition of claim 1 is for compression molding. The resin composition according to claim 15, wherein the component (D) is selected from the difference ΔT (°C) between the mold temperature Tc (°C) during compression molding and the 10-hour half-life temperature T10 (°C) of the (D) component is 20 1 or more types of radical generators within the range of ℃ or higher and 80 ℃ or lower. The resin composition according to claim 1 is for forming an insulating layer. A resin paste comprising the resin composition according to any one of claims 1 to 17. A hardened product, which is a hardened product of the resin composition according to any one of claims 1 to 17 or the resin paste according to claim 18. A resin sheet having a support body, and a resin composition layer comprising the resin composition according to any one of claims 1 to 17 or the resin paste according to claim 18 provided on the support body. A printed wiring board comprising an insulating layer formed of a resin composition as claimed in any one of claims 1 to 17 or a hardened product of a resin paste as claimed in claim 18. A semiconductor chip package comprising the printed wiring board as claimed in claim 21 and a semiconductor chip mounted on the printed wiring board. A semiconductor chip package comprising a semiconductor chip and a resin composition according to any one of claims 1 to 17 or a hardened product of the resin paste according to claim 18 for sealing the semiconductor chip. A semiconductor device comprising a printed wiring board as claimed in claim 21 or a semiconductor chip package as claimed in claim 22 or 23. A method of manufacturing a printed wiring board, comprising: a step of forming a resin composition layer comprising the resin composition according to any one of claims 1 to 17 or a resin composition layer comprising the resin paste according to claim 18 by compression molding on a circuit substrate, and The step of hardening the aforementioned resin composition layer. A method of manufacturing a semiconductor chip package, comprising: On a semiconductor wafer, a step of forming a resin composition layer comprising the resin composition according to any one of claims 1 to 17 or a resin composition layer comprising the resin paste according to claim 18 by compression molding, and The step of hardening the aforementioned resin composition layer.