resin composition

Abstract

The present invention provides a resin composition comprising (A) an epoxy resin, (B) an inorganic filler and (C) an elastomer, wherein the (A) epoxy resin comprises: (A-1) an epoxy resin containing epoxy groups and having a chelate-forming ability.

Description

[Technical Field]

[0001] This invention relates to a resin composition and a cured product using the resin composition, a resin sheet, a circuit board, a semiconductor wafer package, and a semiconductor device. [Previous Technology]

[0002] In recent years, the demand for small, high-performance electronic devices such as smartphones and tablets has increased, leading to a greater demand for high-performance sealing materials used in semiconductor chip packaging for these devices. As such sealing materials, those formed by curing resin compositions are known. On the other hand, technologies for applications different from sealing materials include those in Patent Documents 1 and 2. (Prior Art Documents, Patent Documents)

[0003] Patent Document 1: Japanese Patent Application Publication No. 2018-80221; Patent Document 2: Japanese Patent Publication No. 5491276 [Summary of the Invention]

[0004] The problem that the invention aims to solve

[0005] For purposes such as improving insulation and sealing performance, resin compositions used in sealing materials generally contain inorganic fillers. Cured resin compositions containing inorganic fillers tend to exhibit significant warping.

[0006] Assuming that the hardened material contains a fiber matrix like a prepreg, the overall rigidity of the hardened material can be improved or thermal expansion can be reduced by the effect of the fiber matrix, thus it is believed that warping can be suppressed. However, sealing materials usually do not contain a fiber matrix, so it is difficult to suppress warping.

[0007] Therefore, the inventors attempted to suppress warpage by reducing the elastic modulus of the cured resin composition. Specifically, they attempted to suppress warpage by using a resin composition containing an elastomer and reducing the elastic modulus of its cured form. As a result, warpage suppression was achieved. However, the adhesion between the cured resin composition containing the elastomer and the conductor layer deteriorated.

[0008] Therefore, the inventors further explored the possibility of improving the seal by combining it with an adhesive agent in combination with an elastomer. However, while the seal improved with the adhesive agent, warpage increased. Therefore, existing sealing materials cannot simultaneously achieve warpage suppression and improved seal.

[0009] In view of the above-mentioned problems, the present invention aims to provide a resin composition that yields a cured product with excellent warp suppression and adhesion to a conductor layer, a cured product of the resin composition, and resin sheets, circuit boards, semiconductor wafer packages, and semiconductor devices using the resin composition. Means for solving the problems

[0010] The inventors conducted thorough research to solve the aforementioned problems. As a result, the inventors discovered that the aforementioned problems could be solved by using a resin composition comprising (A) an epoxy resin, (B) an inorganic filler, and (C) an elastomer, wherein (A) the epoxy resin comprises (A-1) an epoxy resin containing epoxy groups and having a chelate-forming ability, thereby completing the present invention. That is, the present invention includes the following contents.

[0011] [1] A resin composition comprising (A) an epoxy resin, (B) an inorganic filler and (C) an elastomer, wherein (A) the epoxy resin comprises (A-1) an epoxy resin containing epoxy groups and having a chelate-forming ability; [2] The composition of [1] wherein the chelate content of component (A-1) is 0.3% to 10% by mass; [3] The resin composition of [1] or [2] wherein the ratio of the mass of component (A-1) W(A-1) to the mass of component (C) W(C) W(A-1) / W(C) is 0.01 to 1.0; [4] The resin composition of any one of [1] to [3] wherein the amount of component (B) relative to 100% by mass of the non-volatile components of the resin composition is 40% by mass or more; [5] [6] A resin composition of any one of [1] to [4], wherein component (C) has a number average molecular weight of 1000 or more; [7] A resin composition of any one of [1] to [5], wherein it further includes (D) a curing agent; [8] A resin composition of any one of [1] to [6], wherein it further includes (E) a curing accelerator; [9] A resin composition of any one of [1] to [8], which is used as a composition sealing layer;

[10] A cured form of a resin composition of any one of [1] to [8];

[11] A resin sheet, wherein it comprises a support and a resin composition layer comprising any one of [1] to [8] formed on the support;

[12] A circuit board, which is a cured form of a resin composition comprising any one of [1] to [8];

[13] A semiconductor wafer package, which is a cured form of a resin composition comprising any one of [1] to [8];

[13] A semiconductor device comprising a circuit board as described in

[11] or a semiconductor wafer package as described in

[12] . Effects of the Invention

[0012] By means of the present invention, it is possible to provide a resin composition that can obtain a cured material with excellent warp suppression and adhesion to the conductor layer, a cured material of the resin composition, and a resin sheet, circuit board, semiconductor wafer package and semiconductor device using the resin composition.

Implementation Method

[0014] Hereinafter, embodiments and examples of the present invention will be described. However, the present invention is not limited to the embodiments and examples shown below, and can be implemented in any way without departing from the scope of the claims and their equivalents. [1. Overview of the resin composition]

[0015] The resin composition according to one embodiment of the present invention comprises (A) an epoxy resin, (B) an inorganic filler, and (C) an elastomer. Furthermore, (A) the epoxy resin comprises (A-1) an epoxy resin containing epoxy groups and having a chelate-forming ability. In the following description, "(A-1) an epoxy resin containing epoxy groups and having a chelate-forming ability" is sometimes referred to as "(A-1) chelate-type epoxy resin". And in the following description, "having a chelate-forming ability" is sometimes referred to as "chelate-capable structure".

[0016] The resin composition of this embodiment can be thermocured to obtain a cured product. Furthermore, the resulting cured product exhibits excellent warpage suppression and adhesion to the conductor layer. Moreover, the cured product of the resin composition of this embodiment generally exhibits excellent adhesion to silicon. Additionally, the resin composition of this embodiment preferably has a low minimum melt viscosity, and preferably yields a cured product with a low tensile modulus.

[0017] The resin composition related to this embodiment may further include any component in combination with the above-described components. For example, the resin composition may include (D) a curing agent, (E) a curing accelerator, etc. [2. (A) Epoxy resin]

[0018] The resin composition related to this embodiment includes epoxy resin (A) as component (A). Epoxy resin (A) is a curable resin having epoxy groups.

[0019] In this embodiment, the epoxy resin (A) contains a chelate-type epoxy resin as component (A-1). The chelate-type epoxy resin contains epoxy groups and chelating ability structures.

[0020] A chelate-forming capability structure refers to a structure having the ability to form chelates. This chelate-forming capability structure typically contains at least one atom selected from oxygen and nitrogen. In the following description, atoms selected from oxygen and nitrogen are sometimes referred to as "specific atoms." A chelate-forming capability structure typically contains multiple specific atoms. These multiple specific atoms are generally not directly bonded; therefore, there are molecular chains connecting these specific atoms to each other. That is, specific atoms are usually linked to each other by molecular chains. Here, the atoms contained in the aforementioned molecular chains do not include oxygen atoms or nitrogen atoms. The number of atoms in the aforementioned molecular chains is typically 1 or more, preferably 2 or more, and preferably 6 or less. Here, the number of atoms in the aforementioned molecular chains that connect specific atoms to each other represents the minimum number of atoms present among the specific atoms linked by the molecular chains. Therefore, even if there are branches bonded to the aforementioned molecular chains, the number of atoms contained in those branches is not included in the number of atoms in the aforementioned molecular chains. Therefore, the chelate-capable structure can be a structure containing specific atoms that are adjacent to each other, preferably separated by one or more but no more than six, and more preferably two or more but no more than six atoms. In this chelate-capable structure, some or all of the specific atoms can function as coordinating atoms.

[0021] Preferably, the chelate-forming structure contains an oxygen atom as a specific atom. More preferably, at least one of the oxygen atoms as a specific atom originates from a hydroxyl group. That is, even more preferably, the chelate-forming structure contains a hydroxyl group, and the oxygen atom contained in the hydroxyl group is a specific atom of the chelate-forming structure. Furthermore, even more preferably, at least one of the oxygen atoms as a specific atom originates from a carbonyl group. That is, even more preferably, the chelate-forming structure contains a carbonyl group, and the oxygen atom contained in the carbonyl group is a specific atom of the chelate-forming structure.

[0022] When the chelate capable structure contains multiple oxygen atoms, it is preferable that these oxygen atoms include oxygen atoms linked by a molecular chain of two atoms. That is, it is preferable that two oxygen atoms in the chelate capable structure are adjacent to each other with a gap of two atoms. The chelate capable structure may contain one group of two adjacent oxygen atoms separated by a gap of two atoms as described above, or it may contain two or more groups of two adjacent oxygen atoms separated by a gap of two atoms as described above.

[0023] The chelate-capable structure typically includes carbon and hydrogen atoms in combination with specific atoms. Furthermore, the chelate-capable structure may also include any heteroatoms other than oxygen and nitrogen atoms. Phosphorus and sulfur atoms are examples of preferred heteroatoms included in the chelate-capable structure. The type of heteroatom may be one or more. The number of heteroatoms may also be one or more.

[0024] Specific examples of preferred chelating structures include carboxyl groups and phosphate groups. Phosphate groups are particularly preferred. The chelating structure can be present at any point in the basic backbone, side chain, or terminal of the (A-1) chelating epoxy resin. The (A-1) chelating epoxy resin may contain one or more chelating structures. Furthermore, the number of chelating structures contained in one molecule of the (A-1) chelating epoxy resin may also be one or more.

[0025] (A-1) The number of epoxy groups contained in one molecule of chelate type epoxy resin can be one or more.

[0026] (A-1) Chelate-type epoxy resins preferably contain aromatic structures in their molecules. Aromatic structures refer to chemical structures generally defined as aromatic, and also include polycyclic aromatics and aromatic heterocycles. Using (A-1) chelate-type epoxy resins containing aromatic ring structures can improve the heat resistance of the cured resin composition.

[0027] (A-1) Chelate-type epoxy resins may include structures obtained by reacting an epoxy resin without chelating ability with a compound containing chelating ability. For example, (A-1) chelate-type epoxy resins containing phosphate groups may include structures obtained by reacting an epoxy resin without chelating ability with a phosphoric acid. Examples of phosphoric acids include phosphoric acid (H3PO4), phosphonic acid (H3PO3), hypophosphoric acid (H3PO2), pyrophosphoric acid (H4P2O7), and polyphosphoric acid such as tripolyphosphoric acid.

[0028] (A-1) Chelate-type epoxy resins can be manufactured, for example, by glycidyl etherification of the hydroxyl groups of a compound having phenolic or alcoholic hydroxyl groups and chelating ability. Furthermore, (A-1) chelate-type epoxy resins can be manufactured, for example, by reacting an epoxy resin without chelating ability with a compound containing chelating ability. As a specific example, (A-1) chelate-type epoxy resins containing phosphate groups can be manufactured by the method described in International Publication No. 2021 / 039380.

[0029] In a method for manufacturing an (A-1) chelate-type epoxy resin comprising reacting an epoxy resin without a chelating ability structure with a compound containing a chelating ability structure, the compound containing a chelating ability structure typically reacts with the epoxy groups of the epoxy resin to obtain the (A-1) chelate-type epoxy resin. In this case, the amount of the compound containing the chelating ability structure reacting is expressed as chelate modification mass. Specifically, chelate modification mass is expressed as the ratio of the compound containing the chelating ability structure reacting with the epoxy resin at 100% by mass relative to the epoxy resin without a chelating ability structure. Preferably, the aforementioned chelate modification mass is 0.3% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.8% by mass or more, more preferably 10% by mass or less, more preferably 5.0% by mass or less, and particularly preferably 3.0% by mass or less. When the chelate modification mass is within the aforementioned range, the adhesion of the cured resin composition can be effectively improved.

[0030] Commercially available products can be used as (A-1) chelate type epoxy resins. Examples of commercially available (A-1) chelate type epoxy resins include "EP-49-10P" and "EP-49-10P2" (both reaction products of bisphenol A type epoxy resin and phosphoric acid) manufactured by ADEKA Corporation, and "EP-49-23" manufactured by ADEKA Corporation.

[0031] (A-1) Chelate type epoxy resins can be used alone or in combination of two or more types.

[0032] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter also referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter also referred to as "solid epoxy resins"). The (A-1) chelate type epoxy resin contained in the resin composition may be only liquid epoxy resin, or only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin. The (A-1) chelate type epoxy resin preferably contains liquid epoxy resin, and more preferably contains only liquid epoxy resin.

[0033] (A-1) The epoxy equivalent of the chelate-type epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 60 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and particularly preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent indicates the mass of resin corresponding to one equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0034] The weight-average molecular weight (Mw) of the (A-1) chelate-type epoxy resin is preferably 100–5000, more preferably 250–3000, and even more preferably 400–1500. Furthermore, the number-average molecular weight of the (A-1) chelate-type epoxy resin is usually less than 5000, preferably less than 3000. The weight-average molecular weight and number-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) and converted to polystyrene values.

[0035] Relative to 100% by mass of the non-volatile components of the resin composition, the amount of (A-1) chelate epoxy resin in the resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. When the amount of (A-1) chelate epoxy resin is within the aforementioned range, it can effectively improve adhesion while suppressing warpage, and can generally effectively reduce the minimum melt viscosity.

[0036] Relative to 100% by mass of the resin composition, the amount of (A-1) chelate epoxy resin in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, particularly preferably 2% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. Unless otherwise specified, the resin composition of the resin composition refers to the non-volatile components of the resin composition other than (B) inorganic filler. When the amount of (A-1) chelate epoxy resin is within the aforementioned range, it can effectively improve adhesion while suppressing warpage, and can generally effectively reduce the minimum melt viscosity.

[0037] Relative to 100% by mass of the total amount of epoxy resin (A), the mass of chelate-type epoxy resin (A-1) is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less. When the amount of chelate-type epoxy resin (A-1) is within the aforementioned range, it can effectively improve adhesion while suppressing warpage, and can generally effectively reduce the minimum melt viscosity.

[0038] The ratio of the mass of the (A-1) chelate-type epoxy resin (W(A-1)) to the mass of the (C) elastomer (W(C)) in the resin composition, W(A-1) / W(C), is preferably within a specific range. Specifically, the aforementioned ratio W(A-1) / W(C) is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.04 or more, preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.7 or less. When the ratio W(A-1) / W(C) is within the aforementioned range, the adhesion can be effectively improved while suppressing warpage, and the minimum melt viscosity can generally be effectively reduced.

[0039] (A) The epoxy resin may be combined with (A-1) chelate-type epoxy resin, and includes: (A-2) an epoxy resin other than (A-1) chelate-type epoxy resin as component (A-2). In the following description, "(A-2) epoxy resin other than (A-1) chelate-type epoxy resin" will also be referred to as "(A-2) any epoxy resin".

[0040] Examples of any epoxy resin in (A-2) 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, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenolnovolac type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, and cresol novolac type epoxy resin. Novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing helical ring, cyclohexane type epoxy resin, cyclohexanediethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylolpropionic acid type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenol benzopyrrolidone type epoxy resin, etc. (A-2) Any epoxy resin may be used alone or in combination of two or more.

[0041] From the viewpoint of obtaining a cured product with good heat resistance, any epoxy resin in (A-2) is preferably an epoxy resin containing an aromatic structure. Examples of any epoxy resin in (A-2) containing an aromatic structure include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenol phenolic varnish type epoxy resin, tert-butylcatechol type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, and glycidylamine type epoxy resin having an aromatic structure. Epoxy resins include cresol-phenolic varnish type, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, butadiene type epoxy resin with aromatic structure, alicyclic epoxy resin with aromatic structure, heterocyclic epoxy resin, helical ring type epoxy resin with aromatic structure, cyclohexanediethanol type epoxy resin with aromatic structure, naphthyl ether type epoxy resin, tris(hydroxymethyl) type epoxy resin with aromatic structure, and tetraphenylethane type epoxy resin with aromatic structure.

[0042] (A-2) Preferably, any epoxy resin comprises an epoxy resin having two or more epoxy groups in one molecule. The proportion of epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the non-volatile component of any epoxy resin in (A-2).

[0043] (A-2) Any epoxy resin may be only liquid epoxy resin, or only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin.

[0044] As a liquid epoxy resin, it is preferred to be a liquid epoxy resin having two or more epoxy groups in one molecule. Examples of preferred liquid epoxy resins that can be used as any epoxy resin in (A-2) include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, phenolic varnish type epoxy resin, cyclohexane type epoxy resin, cyclohexanediethanol type epoxy resin, and epoxy resin having a butadiene structure.

[0045] Specific examples of liquid epoxy resins that can be used as any epoxy resin in (A-2) include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "EPIKOTE828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation. Epoxy resins, including Mitsubishi Chemical Corporation's "jER152" (phenolic varnish type epoxy resin), Mitsubishi Chemical Corporation's "630", "630LSD", and "604" (glycidylamine type epoxy resin), ADEKA Corporation's "ED-523T" (glycirol type epoxy resin), ADEKA Corporation's "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin), and ADEKA Corporation's "EP-4088S". (Dicyclopentadiene type epoxy resin), including "ZX-1059" (a mixture of bisphenol A and bisphenol F type epoxy resins) manufactured by Nippon Steel Chemical Materials Co., Ltd., "PB-3600" manufactured by Daicel Co., Ltd., "JP-100" and "JP-200" (butadiene-structured epoxy resins) manufactured by Nippon Soda Co., Ltd., and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical Materials Co., Ltd. These resins can be used alone or in combination of two or more.

[0046] As a solid epoxy resin, it is preferably a solid epoxy resin having three or more epoxy groups per molecule, and even more preferably an aromatic solid epoxy resin having three or more epoxy groups per molecule. As a preferred solid epoxy resin that can be used as any epoxy resin in (A-2), it is preferably, for example, a bicresin-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol phenolic varnish-type epoxy resin, a cresol phenolic varnish-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenylethane-type epoxy resin, or a phenol benzopyrrolidone-type epoxy resin.

[0047] Specific examples of solid epoxy resins that can be used as any epoxy resin in (A-2) include "HP4032H" (naphthalene-type epoxy resin), "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins), "N-690" (cresol phenolic varnish type epoxy resin), "N-695" (cresol phenolic varnish type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resin), and "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" manufactured by DIC AG. The following epoxy resins are listed: "HP6000L" (naphthyl ether type epoxy resin), "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol phenolic varnish type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC3000H", "NC3000", "NC3000L", "NC3000FH", and "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "ESN475V" and "ESN4100V" (naphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd., and "YX4000H" and "YX4000L" manufactured by Mitsubishi Chemical Co., Ltd. The following resins are available: “X4000”, “YX4000HK”, “YL7890” (bi-xylenol type epoxy resin), “YL6121” (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YX7700” (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “PG-100” and “CG-500” manufactured by Osaka Gas Chemical Co., Ltd., “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1031S” (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and “WHR991S” (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These resins can be used alone or in combination of two or more.

[0048] (A-2) The range of epoxy equivalent of any epoxy resin may be the same as the range of epoxy equivalent of the chelate type epoxy resin in (A-1).

[0049] (A-2) The range of weight-average molecular weight and number-average molecular weight of any epoxy resin may be the same as the range of weight-average molecular weight and number-average molecular weight of chelate-type epoxy resin in (A-1).

[0050] When using liquid epoxy resin and solid epoxy resin in combination as (A) epoxy resin, the mass ratio of them (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:5, more preferably 10:1 to 1:2, and particularly preferably 5:1 to 1:1.

[0051] Relative to 100% by mass of the non-volatile components of the resin composition, the amount of epoxy resin (A) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. When the amount of epoxy resin (A) is within the aforementioned range, warpage suppression and improved adhesion can be significantly obtained, and the minimum melt viscosity can generally be effectively reduced.

[0052] Relative to 100% by mass of the resin component in the resin composition, the amount of (A) epoxy resin in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. When the amount of (A) epoxy resin is within the aforementioned range, the effects of warpage suppression and improved adhesion can be significantly obtained, and the minimum melt viscosity can generally be effectively reduced. [3. (B) Inorganic filler material]

[0053] The resin composition related to this embodiment includes (B) inorganic filler material as component (B). (B) Inorganic filler material is generally contained in the resin composition in the form of particles.

[0054] As the inorganic filler material (B), an inorganic compound is used. Examples of materials that can be used as the inorganic filler material (B) include, for example, silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, gibbsite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon dioxide and alumina are more suitable, and silicon dioxide is particularly suitable. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Furthermore, spherical silicon dioxide is preferred as the silicon dioxide. (B) One type of inorganic filler material may be used alone, or two or more types may be used in combination.

[0055] Commercially available products as (B) inorganic filler materials include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo Co., Ltd., “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd., “YC100C”, “YA050C”, “YA050C-MJE” and “YA010C” manufactured by Yatoma Co., Ltd., “UFP-30” manufactured by DENKA Co., Ltd., “SILFIL NSS-3N”, “SILFIL NSS-4N” and “SILFIL NSS-5N” manufactured by Tokuyama Co., Ltd., and “SC2500SQ”, “SO-C4”, “SO-C2”, “SO-C1” and “SC2050-SXF” manufactured by Yatoma Co., Ltd.

[0056] From the viewpoint of significantly obtaining the desired effect of the present invention, (B) the average particle size of the inorganic filler material is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less.

[0057] (B) The average particle size of the inorganic filler material can be determined by laser diffraction scattering based on the Mie scattering theory. Specifically, a laser diffraction scattering particle size distribution measuring device can be used to generate the particle size distribution of the inorganic filler material on a volume basis, and the median particle size can be used as the average particle size for measurement. The sample to be measured can be obtained by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a tube and dispersing it ultrasonically for 10 minutes. For the sample to be measured, a laser diffraction particle size distribution measuring device can be used, using blue and red light source wavelengths, to measure the volume-based particle size distribution of the inorganic filler material in a flow cell manner, and the average particle size can be calculated based on the obtained particle size distribution as the median particle size. Examples of laser diffraction particle size distribution measuring devices include, for example, the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0058] From the viewpoint of significantly achieving the desired effects of the present invention, (B) the specific surface area of ​​the inorganic filler material is preferably 1 m² / g or more, more preferably 2 m² / g or more, and particularly preferably 3 m² / g or more. There is no particular limitation on the upper limit, but it is preferably 60 m² / g or less, 50 m² / g or less, or 40 m² / g or less. The specific surface area can be measured by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Corporation) according to the BET method, and calculating the specific surface area using the BET multi-point method.

[0059] From the viewpoint of improving moisture resistance and dispersibility, (B) the inorganic filler material is preferably treated with a surface treatment agent. Examples of surface treatment agents include fluorosilane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. One type of surface treatment agent may be used alone, or two or more may be used in any combination.

[0060] Commercially available surface treatment agents include, for example, “KBM403” (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., “KBM-4803” (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0061] From the viewpoint of improving the dispersibility of the inorganic filler material (B), the degree of surface treatment by the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler material is preferably surface treated with 0.2% to 5% by mass of the surface treatment agent, more preferably with 0.2% to 3% by mass of the surface treatment agent, and even more preferably with 0.3% to 2% by mass of the surface treatment agent.

[0062] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content of the inorganic filler per unit surface area. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content of the inorganic filler per unit surface area is preferably 0.02 mg / m² or more, more preferably 0.1 mg / m² or more, and even more preferably 0.2 mg / m² or more. On the other hand, from the viewpoint of suppressing the increase of melt viscosity of the resin composition, it is preferably 1.0 mg / m² or less, more preferably 0.8 mg / m² or less, and even more preferably 0.5 mg / m² or less.

[0063] (B) The carbon content per unit surface area of ​​the inorganic filler material can be determined after cleaning the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, sufficient MEK is added as a solvent to the surface-treated inorganic filler material, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Corporation can be used.

[0064] Relative to 100% by mass of the non-volatile components of the resin composition, the amount of (B) inorganic filler material in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 95% by mass or less, even more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less. Generally, when the amount of inorganic filler material is as high as described above, it is easy to cause an increase in the minimum melt viscosity of the resin composition and a decrease in the adhesion of the cured resin composition. In contrast, with the resin composition related to this embodiment, even when the amount of inorganic filler material is as high as described above, the adhesion of the cured composition can be improved, and the minimum melt viscosity can be further reduced. Therefore, when a larger amount of (B) inorganic filler material is included at or above the aforementioned lower limit value, the advantages of the resin composition related to this embodiment can be particularly effectively utilized. Furthermore, when the amount of inorganic filler material (B) is below the aforementioned upper limit, significant effects of warpage suppression and improved adhesion can be achieved, and the minimum melt viscosity can generally be effectively reduced. [4. (C) Elastomer]

[0065] The resin composition related to this embodiment includes an elastomer (C) as component (C). This elastomer (C) does not contain any substances belonging to components (A) to (B) described above. The elastomer (C) refers to a flexible resin, preferably a resin with rubber elasticity or a resin that exhibits rubber elasticity through polymerization with other components. Examples of rubber elasticity include resins that exhibit an elastic modulus of less than 1 GPa under tensile testing at 25°C and 40% RH according to Japanese Industrial Standard (JISK7161). The elastomer (C) is typically an amorphous resin component soluble in organic solvents. One type of elastomer (C) can be used alone, or two or more can be used in any combination ratio. Using an elastomer (C) can reduce the elastic modulus of the cured resin composition.

[0066] (C) The elastomer is preferably of high molecular weight. (C) The number-average molecular weight (Mn) of the elastomer is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, even more preferably 3000 or more, and particularly preferably 5000 or more. (C) When the elastomer is of the high molecular weight mentioned above, warpage suppression and improved adhesion can be significantly obtained, and the minimum melt viscosity can generally be effectively reduced. There is no particular upper limit to the number-average molecular weight, but it is preferably 1,000,000 or less, and even more preferably 900,000 or less. The number-average molecular weight (Mn) is the number-average molecular weight converted from polystyrene measured using GPC (gel permeation chromatography).

[0067] (C) The elastomer is preferably selected from one or more resins selected from those with a glass transition temperature (Tg) of 25°C or less and those that are liquid at 25°C or less. The glass transition temperature of the resin with a glass transition temperature (Tg) of 25°C or less is preferably 20°C or less, and more preferably 15°C or less. The lower limit of the glass transition temperature is not particularly limited, and is generally -15°C or more. Furthermore, the resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or less, and more preferably a resin that is liquid at 15°C or less. The glass transition temperature can be measured by DSC (differential scanning calorimetry) at a heating rate of 5°C / min.

[0068] (C) The elastomer is preferably a resin having one or more structures selected from the group consisting of polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkyloxyalkylene, polyisoprene, polyisobutylene, polycarbonate, and polystyrene. "(meth)acrylate" is a term encompassing methacrylates and acrylates, as well as combinations thereof. These structures may be contained in the main chain of the molecule of (C) the elastomer or in the side chains.

[0069] Examples of (C) elastomers include resins containing a polybutadiene structure. The polybutadiene structure may be contained in the main chain or in the side chains. Furthermore, the polybutadiene structure may be partially or completely hydrogenated. Resins containing a polybutadiene structure are sometimes referred to as "polybutadiene resins". Specific examples of polybutadiene resins include "Ricon130MA8", "Ricon130MA13", "Ricon130MA20", "Ricon131MA5", "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", and "Ricon184MA6" (polybutadiene containing anhydride groups) manufactured by Cray Valley; "GQ-1000" (polybutadiene with introduced hydroxyl and carboxyl groups), "G-1000", "G-2000", "G-3000" (polybutadiene with two-terminated hydroxyl groups), "GI-1000", "GI-2000", and "GI-3000" (hydrogenated polybutadiene with two-terminated hydroxyl groups) manufactured by Nippon Soda Corporation; and "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation. Furthermore, as a specific example of polybutadiene resin, butadiene resins containing phenolic hydroxyl groups and polyimide resins having a polybutadiene structure, a urethane structure, and a propylene structure within the molecule can be cited. For this polyimide resin, a linear polyimide resin (the polyimide described in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208) can be manufactured using hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetracarboxylic anhydride as raw materials. The butadiene structure content of this polyimide resin is preferably 60% to 95% by mass, and more preferably 75% to 85% by mass. For details regarding this polyimide resin, please refer to the descriptions in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208, which are incorporated herein by reference.

[0070] As an elastomer (C), examples include resins containing a poly(meth)acrylate structure. Resins containing a poly(meth)acrylate structure are sometimes referred to as "poly(meth)acrylate resins". Specific examples of poly(meth)acrylate resins include TEISANRESIN manufactured by Nagase ChemteX Co., Ltd., "ME-2000", "W-116.3", "W-197C", "KG-25", and "KG-3000" manufactured by Nekami Kogyo Co., Ltd., and "ARUFON UH-2000" manufactured by Toa Synthetic Co., Ltd., etc.

[0071] As an elastomer (C), examples include resins containing a polycarbonate structure. Resins containing a polycarbonate structure are sometimes referred to as "polycarbonate resins." Specific examples of polycarbonate resins include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Co., Ltd., and "C-1090," "C-2090," and "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd. Furthermore, specific examples of polycarbonate resins include polyimide resins having an imine structure, a urethane structure, and a polycarbonate structure within the molecule. For such polyimide resins, hydroxyl-terminated polycarbonate, diisocyanate compounds, and tetrabasic anhydrides can be used as raw materials to manufacture linear polyimide resins. The polyimide resin preferably contains 60% to 95% by mass, and more preferably 75% to 85% by mass. For details regarding the polyimide resin, please refer to International Publication No. 2016 / 129541, which is incorporated herein by reference.

[0072] Examples of (C) elastomers include resins containing a polysiloxane structure. Resins containing a polysiloxane structure are sometimes referred to as "siloxane resins." Specific examples of siloxane resins include "SMP-2006," "SMP-2003PGMEA," and "SMP-5005PGMEA" manufactured by Shin-Etsu Chemical Silicon Co., Ltd., and linear polyimides made from amine-terminated polysiloxanes and tetrabasic anhydrides (International Publication No. 2010 / 053185, Japanese Patent Application Publication No. 2002-12667, and Japanese Patent Application Publication No. 2000-319386, etc.).

[0073] As an elastomer (C), examples include resins containing polyalkylene structures and polyalkyleneoxy structures. Resins containing polyalkylene structures are sometimes referred to as "alkylene resins." Furthermore, resins containing polyalkyleneoxy structures are sometimes referred to as "alkyleneoxy resins." The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure with 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure with 3 to 10 carbon atoms, and particularly preferably a polyalkyleneoxy structure with 5 to 6 carbon atoms. Specific examples of alkylene resins and alkyleneoxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Corporation.

[0074] As an elastomer (C), examples include resins containing a polyisoprene structure. Resins containing a polyisoprene structure are sometimes referred to as "isoprene resins". Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

[0075] As an elastomer (C), examples include resins containing a polyisobutylene structure. Resins containing a polyisobutylene structure are sometimes referred to as "isobutylene resins." Specific examples of isobutylene resins include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

[0076] Examples of (C) elastomers include resins containing a polystyrene structure. Resins containing a polystyrene structure are sometimes referred to as "polystyrene resins." Polystyrene resins can be copolymers that combine with styrene units to contain any repeating units different from the aforementioned styrene units, and can also be hydrogenated polystyrene resins. Examples of polystyrene resins include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene-butene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS), styrene-butadiene-butene-styrene block copolymers (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, and styrene-maleic anhydride copolymers. Specific examples of polystyrene resins include hydrogenated styrene thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", and "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "EPOFRIENDAT501" and "CT310" (manufactured by Daicel Corporation); hydroxyl-modified styrene elastomer "SEPTON HG252" (manufactured by Kuraray Corporation); carboxyl-modified styrene elastomer "Tuftec N503M"; amino-modified styrene elastomer "Tuftec N501"; and anhydride-modified styrene elastomer "Tuftec N501". M1913 (manufactured by Asahi Kasei Chemicals Co., Ltd.), unmodified styrene elastomer "SEPTONS8104" (manufactured by Kuraray Co., Ltd.), styrene-ethylene / butene-styrene block copolymer "FG1924" (manufactured by Kraton) and "EF-40" (manufactured by Kraton).

[0077] Of the above, the (C) elastomer is preferably a resin having at least one structure selected from polybutadiene, polycarbonate, and poly(meth)acrylate within its molecule. Furthermore, the (C) elastomer is particularly preferably a resin having a polybutadiene or polycarbonate structure within its molecule. (C) elastomers having a polybutadiene or polycarbonate structure generally have low compatibility with (A-1) chelate-type epoxy resins. Therefore, these (C) elastomers, microscopically separated from the (A-1) chelate-type epoxy resin phase, can form small, flexible domains. In the cured resin composition, the flexibility of these domains is utilized, thereby effectively reducing the elastic modulus of the cured composition, thus particularly effectively suppressing warpage without compromising adhesion.

[0078] (C) The elastomer may have functional groups capable of reacting with (A) epoxy resin. When (C) the elastomer reacts with (A) epoxy resin, the mechanical strength of the cured resin composition can be improved. The functional groups capable of reacting with (A) epoxy resin include functional groups generated by heating. The functional groups capable of reacting with (A) epoxy resin may be one or more functional groups selected from hydroxyl, carboxyl, anhydride, phenolic hydroxyl, epoxy, isocyanate, and urethane groups. Preferably, these functional groups are hydroxyl, anhydride, phenolic hydroxyl, epoxy, isocyanate, and urethane groups; more preferably, they are hydroxyl, anhydride, phenolic hydroxyl, and epoxy groups; particularly preferably, they are phenolic hydroxyl. The number-average molecular weight (Mn) of the (C) elastomer containing the functional groups is preferably 5000 or more.

[0079] Relative to 100% by mass of the non-volatile components of the resin composition, the amount of (C) elastomer in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less. When the amount of (C) elastomer is within the above range, the effects of warpage suppression and improved adhesion can be significantly obtained, and the minimum melt viscosity can generally be effectively reduced.

[0080] Relative to 100% by mass of the resin component in the resin composition, the amount of (C) elastomer in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 80% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass or less. When the amount of (C) elastomer is within the above range, the effects of warpage suppression and improved adhesion can be significantly obtained, and the minimum melt viscosity can generally be effectively reduced. [5. (D) Hardener]

[0081] In the resin composition related to this embodiment, it may be combined with the above-described components (A) to (C) and further include a curing agent (D) as an optional component. The curing agent (D) as component (D) does not contain any components equivalent to those described above (A) to (C). The curing agent (D) may have the function of reacting with the epoxy resin (A) to cure the resin composition.

[0082] Examples of (D) curing agents include phenolic curing agents, naphthol curing agents, reactive ester curing agents, amine curing agents, acid anhydride curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, and thiol curing agents. Among these, phenolic curing agents, naphthol curing agents, and reactive ester curing agents are preferred, and phenolic curing agents and reactive ester curing agents are particularly preferred. One type of (D) curing agent may be used alone, or two or more may be used in combination.

[0083] From the viewpoint of heat resistance and water resistance, a curing agent having a phenolic structure is preferred as both a phenolic curing agent and a naphthol curing agent. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferred, and a phenolic curing agent containing a triazine skeleton is even more preferred.

[0084] Specific examples of phenolic and naphthol-based curing agents include, for instance, “MEH-7700,” “MEH-7810,” “MEH-7851,” and “MEH-8000H” manufactured by Meiji Kasei Corporation; “NHN,” “CBN,” and “GPH” manufactured by Nippon Kayaku Co., Ltd.; and “SN-170,” “SN-180,” “SN-190,” “SN-475,” “SN-485,” “SN-495,” “SN-495V,” “SN-375,” and “SN-395” manufactured by Nippon Steel Chemical Materials Co., Ltd. The products manufactured by DIC Corporation include “TD-2090”, “TD-2090-60M”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018”, “LA-3018-50P”, “EXB-9500”, “HPC-9500”, “KA-1160”, “KA-1163”, and “KA-1165”; while the products manufactured by Qunrong Chemical Corporation include “GDP-6115L”, “GDP-6115H”, and “ELPC75”.

[0085] As an active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among these, compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds, are preferred as active ester curing agents. This active ester curing agent is preferably a compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. Particularly from the viewpoint of improved heat resistance, active ester compounds obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and active ester curing agents obtained from carboxylic acid compounds and phenolic compounds and / or naphthol compounds are even more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type diphenol compounds, and linear phenolic resins. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0086] Preferred examples of active ester curing agents include active ester curing agents containing a dicyclopentadiene-type diphenol structure, active ester curing agents containing a naphthalene structure, active ester curing agents containing an acetylated derivative of a linear phenolic resin, and active ester curing agents containing a benzoyl derivative of a linear phenolic resin. More preferably, active ester curing agents contain a naphthalene structure or active ester curing agents contain a dicyclopentadiene-type diphenol structure. "Dicyclopentadiene-type diphenol structure" refers to a divalent structural unit formed by penephedrine-p-dicyclopentyl-p-p-phenyl.

[0087] Commercially available active ester curing agents include those containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "EXB-8000L-65TM" (manufactured by DIC Corporation), while active ester curing agents containing a naphthalene structure include "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", and "EXB-8150L-65T". Examples of active ester curing agents containing acetylated linear phenolic resins include "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0088] Examples of amine curing agents include those having one or more amino groups within one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Aromatic amines are preferred. The amine curing agent is preferably a primary or secondary amine, and more preferably a primary amine. Specific examples of amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminophen, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylphen, 3,3'-diaminodiphenylphen, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino- 4-Hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl) benzoxide, bis(4-(3-aminophenoxy)phenyl) benzoxide, etc. Amine-based hardeners can be commercially available products, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARDA-A", "KAYAHARDA-B", and "KAYAHARDA-S" manufactured by Nippon Kayaku Co., Ltd., and "EPICUREW" manufactured by Mitsubishi Chemical Co., Ltd.

[0089] Examples of anhydride-based curing agents include curing agents having one or more anhydride groups within one molecule. Specific examples of anhydride-based curing agents include, for instance, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylfluoroantimony sulfonic anhydride, hydrogenated methylfluoroantimony sulfonic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and diphenyltricarboxylic anhydride. Polymer-type acid anhydrides include benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyltrimethyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimethoxybenzoic anhydride ester), and styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available anhydride curing agents include, for example, "MH-700" manufactured by Shin Nippon Rikka Co., Ltd.

[0090] Specific examples of benzoxazine-based hardeners include "JBZ-OD100" (benzoxazine ring equivalent 218 g / eq.), "JBZ-OP100D" (benzoxazine ring equivalent 218 g / eq.), and "ODA-BOZ" (benzoxazine ring equivalent 218 g / eq.) manufactured by JFE Chemical Co., Ltd.; "Pd" (benzoxazine ring equivalent 217 g / eq.) and "Fa" (benzoxazine ring equivalent 217 g / eq.) manufactured by Shikoku Chemical Industry Co., Ltd.; and "HFB2006M" (benzoxazine ring equivalent 432 g / eq.) manufactured by Showa Polymer Co., Ltd.

[0091] Examples of difunctional cyanate resins include bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylene-1,5-phenyl cyanate), 4,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate-phenyl)propane, 1,1-bis(4-cyanate-phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate-phenyl-1-(methylethylidene))benzene, bis(4-cyanate-phenyl) sulfide, and bis(4-cyanate-phenyl) ether; polyfunctional cyanate resins derived from phenolic varnish resins and cresol varnish resins; prepolymers obtained by partially triazinizing these cyanate resins; etc. Specific examples of cyanate ester resins include "PT30" and "PT60" (phenolic varnish type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers obtained by triazinizing part or all of bisphenol A dicyanate to form a trimer), etc., manufactured by Lonza Japan Co., Ltd.

[0092] Specific examples of carbodiimide curing agents include CARBODILITE (registered trademark) V-03 (carbodiimide equivalent: 216 g / eq.), V-05 (carbodiimide equivalent: 262 g / eq.), V-07 (carbodiimide equivalent: 200 g / eq.), and V-09 (carbodiimide equivalent: 200 g / eq.) manufactured by Nisshin Chemical Co., Ltd., and Stabaxol (registered trademark) P (carbodiimide equivalent: 302 g / eq.) manufactured by Rhein Chemical Co., Ltd.

[0093] Specific examples of thiol curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0094] (D) The active group equivalent of the hardener is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent is the mass of hardener corresponding to 1 equivalent of active group.

[0095] When the number of epoxy groups in (A) epoxy resin is set to 1, the number of active groups in (D) curing agent is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, preferably 5.0 or less, more preferably 2.0 or less, and particularly preferably 1.0 or less. "Number of epoxy groups in (A) epoxy resin" refers to the sum of values ​​obtained by dividing the mass of the non-volatile component of (A) epoxy resin present in the resin composition by the epoxy equivalent. Furthermore, "number of active groups in (D) curing agent" refers to the sum of values ​​obtained by dividing the mass of the non-volatile component of (D) curing agent present in the resin composition by the active group equivalent.

[0096] Relative to 100% by mass of the non-volatile components of the resin composition, the amount of (D) curing agent in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 4% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

[0097] Relative to 100% by mass of the resin component in the resin composition, the amount of (D) curing agent in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 15% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. [6. (E) Curing accelerator]

[0098] In the resin composition related to this embodiment, (E) curing accelerator may be further included as an arbitrary component in combination with the above-described components (A) to (D). The (E) curing accelerator, as component (E), does not include those belonging to the above-described components (A) to (D). The (E) curing accelerator functions as a curing catalyst that promotes the curing of the (A) epoxy resin.

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

[0100] As a phosphorus-based curing accelerator, examples include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic tert-butylphosphonium, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, and tetraphenylphosphonium bromide. Aromatic phosphonium salts including p-tolyltriphenylphosphonium tetrap-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tri(3-methylphenyl)ethylphosphonium tetraphenylborate, tri(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, etc. Aliphatic phosphines such as di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyl diphenylphosphine, ethyl diphenylphosphine, butyl diphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6 ... Aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0101] As urea-based hardening accelerators, examples include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)- Aromatic dimethylureas include 1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-epenylphenyl)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-epenylphenyl)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc.

[0102] As guanidine hardening promoters, examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc.

[0103] Examples of imidazole hardening accelerators include, for example, 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolium-( [1')]-Ethyl-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds with epoxy resins. Commercially available imidazole hardening accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "C11Z", "C11Z-CN", "C11Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.

[0104] Examples of metal curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as acetoacetone cobalt(II) and acetoacetone cobalt(III), organocopper complexes such as acetoacetone copper(II), organozinc complexes such as acetoacetone zinc(II), organoiron complexes such as acetoacetone iron(III), organonickel complexes such as acetoacetone nickel(II), and organomanganese complexes such as acetoacetone manganese(II). Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0105] Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene. Commercially available products can be used as amine curing accelerators, such as "MY-25" manufactured by Ajinomoto Fine Chemicals Co., Ltd.

[0106] Relative to 100% by mass of the non-volatile components of the resin composition, the amount of (E) curing accelerator in the resin composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.

[0107] Relative to 100% by mass of the resin component in the resin composition, the amount of (E) curing accelerator in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.10% by mass or more, preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less. [7. (F) Any additives]

[0108] The resin composition related to this embodiment may be combined with components (A) to (E) above, and further include any additive (F) as any non-volatile component. Examples of any additive (F) include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; leveling agents such as organosilicon leveling agents and acrylic polymer leveling agents; tackifiers such as bentonite and montmorillonite; defoamers such as organosilicon defoamers, acrylic defoamers, fluorinated defoamers, and vinyl resin defoamers; ultraviolet absorbers such as benzotriazole ultraviolet absorbers; adhesion enhancers such as ureasilane; adhesion enhancers such as triazole adhesion enhancers, tetraazole adhesion enhancers, and triazine adhesion enhancers; antioxidants such as hindered phenolic antioxidants; fluorescent whitening agents such as zirconia derivatives; and fluorinated surfactants. Surfactants such as surfactants, organosilicone surfactants, etc.; phosphorus flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus); nitrogen flame retardants (e.g., melamine sulfate); halogen flame retardants; inorganic flame retardants (antimony trioxide), etc.; dispersants such as phosphate esters, polyoxyethylene dispersants, acetylene dispersants, organosilicone dispersants, anionic dispersants, cationic dispersants, etc.; stabilizers such as borate esters, titanate esters, aluminate esters, zirconate esters, isocyanate esters, carboxylic acids, and carboxylic anhydrides. (F) Any additive may be used alone or in combination of two or more. [8. (G) Solvents]

[0109] In the resin composition related to this embodiment, it may be combined with the non-volatile components (A) to (F) mentioned above to further include solvent (G) as an arbitrary volatile component. As solvent (G), an organic solvent is typically used. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; and 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and carbitol acetate. Ether ester solvents such as diglycolAcetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); acetamide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; arginine solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (G) One solvent may be used alone, or two or more solvents may be used in combination.

[0110] (G) The amount of solvent is not particularly limited. When all components in the resin composition are set as 100% by mass, it can be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or even 0% by mass. [9. Method for manufacturing resin composition]

[0111] The resin composition related to this embodiment can be manufactured, for example, by mixing the above-mentioned components. The above-mentioned components can be mixed partially or completely simultaneously, or they can be mixed sequentially. During the mixing of each component, the temperature can be appropriately set, so heating and / or cooling can be performed temporarily or continuously. Furthermore, stirring or agitation can be performed during the mixing of each component. [10. Characteristics of the resin composition and its cured product]

[0112] Using the resin composition related to this embodiment, a hardened material capable of suppressing warpage can be obtained. Therefore, when a laminate is obtained by forming a layer of hardened resin composition (hereinafter also referred to as "hardened layer") on a substrate such as a silicon wafer, the warpage of the laminate can be reduced. For example, when the laminate is manufactured by the method described in the [Warpage Evaluation] section of the following embodiments and its warpage is measured, the warpage can be reduced to 1.5 mm or less.

[0113] The resin composition of this embodiment can be used to obtain a hardened material with excellent adhesion to the conductor layer. Therefore, when the hardened layer of the resin composition is formed in contact with the conductor layer, peeling between the conductor layer and the hardened layer can be suppressed. For example, when the copper foil adhesion strength is measured by the method described in the [Evaluation of Copper Foil Adhesion Strength] section of the following embodiment, a copper foil adhesion strength of 0.53 kgf / cm or more, 0.57 kgf / cm or more, and 0.60 kgf / cm or more can be obtained.

[0114] With the resin composition related to this embodiment, a hardened material with excellent adhesion to silicon can generally be obtained. Therefore, when a hardened layer of the resin composition is formed in contact with a component formed of silicon, peeling between the component and the hardened layer can be suppressed. For example, when the Si adhesion strength is measured by the method described in the [Evaluation of Si Adhesion Strength] section of the following embodiments, a Si adhesion strength of 550 kgf / cm² or more can be obtained, more preferably 570 kgf / cm² or more, and particularly preferably 590 kgf / cm² or more.

[0115] With the resin composition related to this embodiment, a hardened material with a low modulus of elasticity can generally be obtained. The inventors believe that the hardened material having such a low modulus of elasticity is one of the reasons for obtaining the excellent adhesion and warp suppression effects described above. For example, when the tensile modulus of the hardened material of the resin composition is measured by the method described in the [Measuring Modulus of Elasticity] section of the following embodiments, a tensile modulus of elasticity of preferably 16 GPa or less, more preferably 15 GPa or less, and particularly preferably 14.5 GPa or less can be obtained. The lower limit is not particularly limited, for example, it can be 5 GPa or more.

[0116] The resin composition used in this embodiment typically has a low minimum melt viscosity. Therefore, when sealing with the resin composition, the formation of gaps not filled with the resin composition can be suppressed. For example, when the minimum melt viscosity of the resin composition is measured by the method described in the [Measuring Melt Viscosity] section of the following embodiments, a minimum melt viscosity of preferably 9000 poise or less, more preferably 8000 poise or less, and particularly preferably 7500 poise or less can be obtained. The lower limit value is not particularly limited, but it can preferably be 500 poise or more, more preferably 1000 poise or more, and particularly preferably 2000 poise or more.

[0117] The composition has the above-described characteristics, and therefore can be suitably used as a resin composition for sealing layers, particularly as a resin composition for sealing semiconductors (resin composition for semiconductor sealing), and preferably as a resin composition for sealing semiconductor wafers (resin composition for semiconductor wafer sealing). Furthermore, in addition to sealing applications, the resin composition can also be used as a resin composition for insulating layers. For example, the aforementioned resin composition can be suitably used as a resin composition for forming an insulating layer for semiconductor wafer packages (resin composition for insulating layers of semiconductor wafer packages) and as a resin composition for forming an insulating layer for circuit boards (including printed wiring boards) (resin composition for insulating layers of circuit boards).

[0118] Semiconductor wafer packaging can include, for example, FC-CSP, MIS-BGA packaging, ETS-BGA packaging, fan-out WLP (Wafer Level Package), fan-in WLP, fan-out PLP (Panel Level Package), and fan-in PLP.

[0119] Furthermore, the aforementioned resin composition can also be used as an underfill material, for example, as a material for MUF (Molding Underfill) used after a semiconductor wafer is attached to a substrate.

[0120] Furthermore, the aforementioned resin composition can also be used in a wide range of applications employing resin compositions, such as resin sheets, prepregs and other sheet-like laminated materials, solder resists, wafer bonding materials, via-filling resins, and component embedding resins. [11. Resin Sheets]

[0121] One embodiment of the present invention relates to a resin sheet having a support and a resin composition layer formed on the support. The resin composition layer is a layer formed by a resin composition, and therefore typically contains the above-described resin composition, preferably containing only the above-described resin composition.

[0122] From the viewpoint of thinness, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, and even more preferably 500 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, or 200 μm or less. There is no particular limitation on the lower limit of the resin composition layer thickness; for example, it can be 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0123] As a support, examples include films formed of plastic materials, metal foils, and release paper, with films or metal foils formed of plastic materials being more preferred.

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

[0125] When using a metal foil as a support, examples of metal foils include copper foil and aluminum foil. Among these, copper foil is preferred. As copper foil, foil formed from copper as a single metal can be used, or foil formed from an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0126] The support may be treated with matte finish, corona discharge treatment, antistatic treatment, etc. on the surface that is bonded to the resin composition layer.

[0127] Furthermore, as a support, a support with a release layer that has a release layer on the surface bonded to the resin composition layer can be used. Examples of release agents for the release layer of a support with a release layer include, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available release agents include, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, which are alkyd resin release agents. Examples of supports with a release layer include, for example, "LUMIRROR T60" manufactured by Toray Industries, Ltd., "Purex" manufactured by Teijin Corporation, and "Unipeel" manufactured by Unikica Corporation.

[0128] The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, the overall thickness of the support with the release layer is preferably within the above range.

[0129] Resin flakes can be manufactured, for example, by coating a resin composition onto a support using a die coater or similar coating apparatus. Alternatively, the resin composition can be dissolved in a solvent to create a resin varnish, which is then applied to manufacture the resin flakes. By using a solvent, the viscosity can be adjusted, improving coatability. When using a resin varnish, it is typically dried after coating to form a resin composition layer.

[0130] As a solvent, for example, a solvent that can be contained in the resin composition can be used. One solvent can be used alone, or two or more solvents can be used in any ratio.

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

[0132] The resin sheet may include any layer other than the support and the resin composition layer, as needed. For example, in the resin sheet, a protective film, depending on the support, may be provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film prevents dirt or other contaminants from adhering to the surface of the resin composition layer or causing damage. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. Furthermore, the resin sheet can be rolled up for storage.

[0133] The resin sheet can be suitably used for sealing semiconductor wafers (resin sheet for sealing semiconductor wafers). Examples of suitable semiconductor wafer packages include, for example, fan-out type WLP, fan-in type WLP, fan-out type PLP, and fan-in type PLP. Furthermore, the resin sheet can be used, for example, for sealing circuit boards (resin sheet for sealing circuit boards).

[0134] Furthermore, the resin sheet can be well used to form an insulating layer in the manufacture of semiconductor wafer packages (insulating resin sheet for semiconductor wafer packages). For example, the resin sheet can be used to form an insulating layer for a circuit board (insulating resin sheet for a circuit board). Examples of packages using such a substrate include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

[0135] Furthermore, resin sheets can also be used as materials for MUFs used after semiconductor wafers are attached to a substrate.

[0136] Furthermore, resin sheets can be used in a wide range of other applications requiring high insulation reliability. For example, resin sheets are well-suited for forming insulating layers on circuit boards such as printed wiring boards. [12. Circuit Boards]

[0137] A circuit board according to one embodiment of the present invention includes a cured resin composition. Typically, the circuit board includes a cured layer formed from the cured resin composition. This cured layer typically functions as an insulating layer or a sealing layer, preferably as a sealing layer. The circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2): (1) forming a resin composition layer on a substrate; (2) curing the resin composition layer to form a cured layer.

[0138] In step (1), a substrate is prepared. Examples of substrates include glass epoxy boards, metal substrates (stainless steel and cold-rolled steel sheets (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Furthermore, the substrate may have a metal layer such as copper foil on its surface as part of the substrate. For example, a substrate with a peelable first metal layer and a second metal layer on both surfaces can be used. When such a substrate is used, a conductor layer that can function as a wiring layer for circuit wiring is usually formed on the side of the second metal layer opposite to the first metal layer. Examples of materials for the metal layer include copper foil, copper foil with a carrier, and materials for the conductor layer described later, with copper foil being preferred. Examples of substrates with metal layers include the "Micro Thin" ultra-thin copper foil with a carrier copper foil manufactured by Mitsui Metals & Mining Co., Ltd.

[0139] Furthermore, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, the component comprising the substrate and the conductor layer formed on the surface of the substrate is sometimes appropriately referred to as a "substrate with a wiring layer". As the conductor material contained in the conductor layer, examples include materials containing one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductor material, a single metal or an alloy may be used. As an alloy, examples include alloys of two or more metals selected from the above metals (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoint of versatility in conductor layer formation, cost, and ease of pattern formation, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and alloys such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy as alloys are preferred. Among these, the preferred materials are single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and nickel-chromium alloys, especially copper.

[0140] For the conductor layer, for example, it may be patterned to function as a wiring layer. In this case, the linewidth (circuit width) / line spacing (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20 / 20 μm or less (i.e., the pitch is 40 μm or less), even more preferably 10 / 10 μm or less, further preferably 5 / 5 μm or less, even more preferably 1 / 1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch may be uniform or non-uniform throughout the conductor layer. The minimum pitch of the conductor layer may, for example, be 40 μm or less, 36 μm or less, or 30 μm or less.

[0141] The thickness of the conductor layer varies depending on the design of the circuit board, preferably 3μm to 35μm, more preferably 5μm to 30μm, even more preferably 10μm to 20μm, and particularly preferably 15μm to 20μm.

[0142] After preparing the substrate, a resin composition layer is formed on the substrate. When a conductor layer is formed on the surface of the substrate, the formation of the resin composition layer is preferably carried out by embedding the conductor layer into the resin composition layer.

[0143] The resin composition layer is formed, for example, by laminating a resin sheet to a substrate. This lamination can be performed, for example, by heating and pressing the resin sheet onto the substrate from the support side to bond the resin composition layer to the substrate. Examples of components for heating and pressing the resin sheet onto the substrate (hereinafter also referred to as "heat-pressing components") include, for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller, etc.). Furthermore, it is preferable not to press the heat-pressing component directly onto the resin sheet, but to apply pressure through an elastic material such as heat-resistant rubber, so that the resin sheet fully conforms to the surface of the substrate and becomes uneven.

[0144] The lamination of the substrate and the resin sheet can be carried out, for example, by vacuum lamination. The lamination conditions can be, for example, as follows: The heat-pressing temperature is preferably in the range of 60°C to 160°C, and more preferably in the range of 80°C to 140°C. The heat-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 heat-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 conditions of 13 hPa or less.

[0145] After lamination, the laminated resin sheet can be smoothed under normal pressure (atmospheric pressure), for example, by applying pressure from the support side to the heated pressing member. The pressure conditions for the smoothing treatment can be the same as the heating and pressing conditions for the lamination described above. Furthermore, the lamination and smoothing treatment can be performed continuously using a vacuum laminator.

[0146] After forming a resin composition layer on a substrate, the resin composition layer is thermocured to form a cured layer. The thermocure conditions of the resin composition layer may vary depending on 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 150°C to 220°C, and even more preferably in the range of 170°C to 200°C. The curing time is in the range of 5 minutes to 120 minutes, preferably in the range of 10 minutes to 100 minutes, and even more preferably in the range of 15 minutes to 90 minutes.

[0147] Before heat 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. For example, before heat curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C or higher but less than 120°C, preferably 60°C or higher but less than 110°C, and even more preferably 70°C or higher but less than 100°C for a period of 5 minutes or more, preferably 5 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0148] By performing the above operations, a circuit board having a cured layer formed from a cured resin composition can be manufactured. Furthermore, the method for manufacturing the circuit board may further include any step. For example, when manufacturing the circuit board using a resin sheet, the method may include a step of peeling off a support from the resin sheet. The support may be peeled off before or after the thermal curing of the resin composition layer.

[0149] The method for manufacturing a circuit board may include, for example, a step of polishing the surface of the hardened layer after forming a hardened layer. The polishing method is not particularly limited. Examples of polishing methods include chemical mechanical polishing using a chemical mechanical polishing apparatus, mechanical polishing methods such as polishing, and surface grinding methods using a rotating grinding wheel.

[0150] A method for manufacturing a circuit board may include, for example, a step of through-hole connection to perform interlayer bonding of conductor layers. As a method of interlayer bonding, an example is the method of creating holes in a hardened layer. By creating holes, vias, or other openings can be formed in the hardened layer. Examples of methods for forming vias include laser irradiation, etching, and mechanical drilling. The size and shape of the vias can be appropriately determined according to the design of the circuit board. Furthermore, through-hole connection can be performed by grinding or polishing the hardened layer.

[0151] After the via is formed, it is preferable to perform a step to remove contaminants from the via. This step is sometimes referred to as a decontamination step. For example, when a conductor layer is formed on a hardened layer by a plating step, a wet decontamination treatment can be performed on the via. Furthermore, when a conductor layer is formed on a hardened layer by a plating step, a dry decontamination step such as a plasma treatment step can be performed. In addition, the hardened layer can be roughened by the decontamination step.

[0152] Furthermore, the hardened layer can be roughened before forming the conductor layer on the hardened layer. This roughening process typically roughens the surface of the hardened layer, including the vias. Both dry and wet roughening processes can be performed. Examples of dry roughening processes include plasma treatment. Examples of wet roughening processes include a method that sequentially performs a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution.

[0153] After forming the via, a conductor layer can be formed on the hardened layer. By forming a conductor layer at the location where the via is formed, the newly formed conductor layer and the conductor layer on the substrate surface will be connected, achieving interlayer bonding. Methods for forming the conductor layer include, for example, plating, evaporation, etc. For example, a conductor layer with a desired wiring pattern can be formed by plating on the surface of the hardened layer using appropriate methods such as semi-additive or fully additive methods. Furthermore, if the support in the resin film is a metal foil, a conductor layer with a desired wiring pattern can be formed by a subtractive method. The material of the formed conductor layer can be a single metal or an alloy. Moreover, the conductor layer can have a single-layer structure or a multi-layer structure containing two or more layers of different types of materials.

[0154] Hereinafter, an example of an embodiment in which a conductor layer is formed on a hardened layer will be described in detail. A plating sheet layer is formed on the surface of the hardened layer by electroless plating. Next, a photomask pattern is formed on the formed plating sheet layer, corresponding to the desired wiring pattern, exposing a portion of the plating sheet layer. After an electroplated layer is formed on the exposed plating sheet layer by electroplating, the photomask pattern is removed. Then, the unwanted plating sheet layer is removed by etching or other processes, thereby forming a conductor layer having the desired wiring pattern.

[0155] The method for manufacturing a circuit board may include a step (4) of removing a substrate. By removing the substrate, a circuit board having a hardened layer and a conductor layer embedded in the hardened layer is obtained. This step (4) may be performed, for example, using a substrate having a peelable metal layer. [13. Semiconductor wafer packaging]

[0156] A semiconductor wafer package according to one embodiment of the present invention comprises a cured form of a resin composition. Examples of such semiconductor wafer packages are as follows.

[0157] The first related semiconductor wafer package includes the aforementioned circuit substrate and a semiconductor wafer mounted on the circuit substrate. The semiconductor wafer package can be manufactured by bonding the semiconductor wafer to the circuit substrate.

[0158] The bonding conditions between the circuit board and the semiconductor wafer can be any conditions that allow for the conductive connection of the terminal electrodes of the semiconductor wafer to the circuit wiring of the circuit board. For example, the conditions used in flip-chip mounting of semiconductor wafers can be used. Furthermore, for example, bonding can be performed with an insulating adhesive between the semiconductor wafer and the circuit board.

[0159] As an example of a bonding method, a method of pressing a semiconductor wafer onto a circuit board can be cited. As for the pressing conditions, the pressing temperature is usually in the range of 120°C to 240°C, preferably in the range of 130°C to 200°C, and even more preferably in the range of 140°C to 180°C, and the pressing time is usually in the range of 1 second to 60 seconds, preferably in the range of 5 seconds to 30 seconds.

[0160] Furthermore, as another example of the bonding method, a method of bonding a semiconductor wafer to a circuit board by reflow soldering can be cited. The reflow conditions can be set in the range of 120°C to 300°C.

[0161] After bonding the semiconductor wafer to the circuit board, the semiconductor wafer can be filled with a molding underfill material. Preferably, the molding underfill material is a resin composition related to the above-described embodiment.

[0162] The second related semiconductor wafer package includes a semiconductor wafer and a cured resin composition that seals the semiconductor wafer. In such a semiconductor wafer package, the cured resin composition typically functions as a sealing layer. Examples of the second related semiconductor wafer package include, for example, a fan-out type WLP and a fan-out type PLP.

[0163] FIG1 is a schematic cross-sectional view showing an example of a fan-out type WLP semiconductor wafer package related to one embodiment of the present invention. For example, as shown in FIG1, the semiconductor wafer package 100 as a fan-out type WLP includes: a semiconductor wafer 110, a sealing layer 120 formed to cover the periphery of the semiconductor wafer 110, a redistribution layer 130 provided on the semiconductor wafer 110 on the side opposite to the sealing layer 120 and serving as an insulating layer, a redistribution layer 140 serving as a conductor layer, a solder mask layer 150, and bumps 160.

[0164] Such a semiconductor wafer package manufacturing method includes: (A) a step of depositing a temporary fixing film on a substrate; (B) a step of temporarily fixing a semiconductor wafer onto the temporary fixing film; (C) a step of forming a sealing layer on the semiconductor wafer; (D) a step of peeling the substrate and the temporary fixing film from the semiconductor wafer; (E) a step of forming a rewiring layer on the surface of the semiconductor wafer where the substrate and the temporary fixing film have been peeled off; (F) a step of forming a rewiring layer as a conductor layer on the rewiring layer; and (G) a step of forming a solder mask layer on the rewiring layer. Furthermore, the above-described semiconductor wafer package manufacturing method may include: (H) a step of dicing multiple semiconductor wafer packages into individual semiconductor wafer packages for monolithic packaging. (Step (A))

[0165] Step (A) is the step of depositing a temporary fixing film on the substrate. The deposition conditions of the substrate and the temporary fixing film can be the same as the deposition conditions of the substrate and the resin film in the method for manufacturing a circuit board.

[0166] As a substrate, examples include: silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates obtained by infiltrating glass fibers with epoxy resin and then subjecting them to heat curing treatment; and substrates formed from bismaleimide triazine resins such as BT resin.

[0167] The temporary fixing film can be made of any material that can be peeled off from the semiconductor wafer and can temporarily fix the semiconductor wafer. Examples of commercially available products include "REVALPHA" manufactured by Nitto Denko Corporation. (Step (B))

[0168] Step (B) is the step of temporarily fixing the semiconductor wafer onto the temporary fixing film. Temporary fixing of the semiconductor wafer can be performed using devices such as flip chip bonders or die bonders. The layout and number of semiconductor wafers can be appropriately set according to the shape and size of the temporary fixing film, the production quantity of the target semiconductor wafer package, etc. For example, the semiconductor wafers can be arranged in a matrix of multiple rows and columns for temporary fixing. (Step (C))

[0169] Step (C) is the step of forming a sealing layer on the semiconductor wafer. The sealing layer may be formed from a cured form of the resin composition related to the above embodiments. The sealing layer is generally formed by a method including the step of forming a resin composition layer on the semiconductor wafer and the step of thermally curing the resin composition layer to form a cured layer as the sealing layer. Regarding the formation of the resin composition layer on the semiconductor wafer, for example, except that a semiconductor wafer is used instead of a substrate, it may be performed by a method similar to the method for forming a resin composition layer on a substrate described in the above-described method for manufacturing a circuit board.

[0170] After forming a resin composition layer on a semiconductor wafer, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor wafer. This seals the semiconductor wafer based on the cured resin composition. The thermal curing conditions of the resin composition layer can be the same as those used in the method for manufacturing a circuit board. Furthermore, before thermally curing the resin composition layer, a preheating treatment can be applied by heating the resin composition layer at a temperature lower than the curing temperature. The preheating treatment conditions can be the same as those used in the preheating treatment method for manufacturing a circuit board. (Step (D))

[0171] Step (D) is the step of peeling the substrate and the temporary fixing film from the semiconductor wafer. The peeling method is preferably a suitable method adapted to the material of the temporary fixing film. Examples of peeling methods include heating, foaming, or expanding the temporary fixing film. Furthermore, examples of peeling methods include irradiating the temporary fixing film with ultraviolet light through the substrate to reduce the adhesive force of the temporary fixing film.

[0172] In methods of heating, foaming, or expanding the temporary fixation film, the heating conditions are typically heating at 100°C to 250°C for 1 to 90 seconds or 5 to 15 minutes. Furthermore, in methods of peeling off the temporary fixation film by reducing its adhesive strength through ultraviolet irradiation, the ultraviolet irradiation dose is typically 10 mJ / cm² to 1000 mJ / cm².

[0173] If the substrate and temporary fixing film are peeled off from the semiconductor wafer as described above, the surface of the sealing layer is exposed. The semiconductor wafer packaging manufacturing method may include a step of polishing the exposed surface of the sealing layer. Polishing can improve the smoothness of the sealing layer surface. As the polishing method, the same method described in the circuit board manufacturing method can be used. (Step (E))

[0174] Step (E) is a step of forming a rewiring layer as an insulating layer on the surface of the semiconductor wafer where the substrate and temporary fixing film have been stripped. Typically, this rewiring layer is formed on the semiconductor wafer and the sealing layer. The rewiring layer may be formed, for example, from a photosensitive resin composition or a thermosetting resin composition. Furthermore, after forming the rewiring layer, vias are typically formed in the rewiring layer to enable interlayer bonding between the semiconductor wafer and the rewiring layer. (Step (F))

[0175] Step (F) is the step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method for forming the rewiring layer on the rewiring forming layer can be the same as the method for forming a conductor layer on a hardened layer in the circuit board manufacturing method. Furthermore, steps (E) and (F) can be performed repeatedly, alternately stacking the rewiring layer and the rewiring forming layer. (Step (G))

[0176] Step (G) is the step of forming a solder mask layer on the rewiring layer. The solder mask layer can be made of any insulating material. From the viewpoint of ease of manufacturing semiconductor wafer packages, a photosensitive resin composition and a thermosetting resin composition are preferred.

[0177] Furthermore, in step (G), bump machining can be performed as needed to form bumps. Bump machining can be performed using methods such as solder balls or solder plating. Additionally, the formation of through-holes during bump machining can be performed in the same manner as in step (E). (Step (H))

[0178] The method for manufacturing semiconductor wafer packages may include steps (A) to (G) and also step (H). Step (H) is a step of dicing multiple semiconductor wafer packages into individual semiconductor wafer packages for monolithic processing. There is no particular limitation on the method of dicing semiconductor wafer packages into individual semiconductor wafer packages.

[0179] As a third example of related semiconductor wafer packaging, an example of semiconductor wafer packaging 100 shown in FIG1 is provided, in which a rewiring layer 130 or a solder resist layer 150 is formed by curing a resin composition related to the above-described embodiment. [14. Semiconductor device]

[0180] One embodiment of the present invention relates to a semiconductor device comprising the circuit board or semiconductor wafer package described above. Examples of semiconductor devices include those used in electrical products (e.g., computers, mobile phones, smartphones, tablets, wearable devices, digital cameras, medical devices, and televisions) and vehicles (e.g., locomotives, automobiles, trams, ships, and airplanes). Embodiments

[0181] Hereinafter, embodiments are shown to specifically describe the present invention. However, the present invention is not limited to the embodiments shown below. In the following description, unless otherwise explained, "parts" and "%" refer to "parts by mass" and "% by mass," respectively. Furthermore, unless otherwise specified, the temperature and pressure conditions are room temperature (25°C) and atmospheric pressure (1 atm). [Description of Inorganic Filler Materials]

[0182] The inorganic filler materials used in the following examples and comparative examples are as described above; Inorganic filler material 1: Spherical silica particles (average particle size 1 μm, specific surface area 4.5 m² / g) surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Industry Co., Ltd. "KBM573"); Inorganic filler material 2: Spherical alumina particles (average particle size 1.5 μm, specific surface area 1.6 m² / g) surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Industry Co., Ltd. "KBM573"). [Manufacturing Example 1. Manufacturing of Elastomer 1]

[0183] In a reaction vessel, 69 g of difunctional hydroxyl-terminated polybutadiene (number-average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1800 g / eq., solid content 100% by mass, manufactured by Nippon Soda Co., Ltd., "G-3000"), 40 g of aromatic hydrocarbon mixed solvent (manufactured by Ipzole 150, manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurylate were mixed and dissolved uniformly. After becoming homogeneous, the temperature was raised to 50°C, and then 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan Co., Ltd., IPDI, isocyanate group equivalent = 113 g / eq) was added while stirring, and the reaction was carried out for about 3 hours. Next, after cooling the reactant to room temperature, 23g of cresol phenolic resin (DIC AG "KA-1160", hydroxyl equivalent = 117 g / eq.) and 60g of diethylene glycol monoethyl ether acetate (Daicel AG) were added. The mixture was stirred and heated to 80°C for approximately 4 hours. The disappearance of the NCO peak at 2250 cm⁻¹ was confirmed by FT-IR. Based on the confirmation of the NCO peak disappearance, this was considered the endpoint of the reaction. The reactant was cooled to room temperature and filtered through a 100-mesh filter cloth to obtain elastomer 1 (50% by mass of non-volatile component) with a polybutadiene structure and phenolic hydroxyl groups. The number average molecular weight was 5500. [Manufacturing Example 2. Manufacturing of Elastomer 2]

[0184] In a reaction vessel, 50 g of difunctional hydroxyl-terminated polybutadiene (number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1800 g / eq., solid content 100% by mass, manufactured by Nippon Soda Co., Ltd., "G-3000"), 23.5 g of aromatic hydrocarbon mixed solvent (manufactured by Idemitsu Petrochemical Co., Ltd., "Ipzole 150"), and 0.005 g of dibutyltin laurylate were mixed and dissolved uniformly. After becoming homogeneous, the temperature was raised to 50°C, and then 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq) was added while stirring, and the reaction was carried out for about 3 hours. Next, after cooling the reactants to room temperature, 8.96 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and 40.4 g of diethylene glycol monoethyl ether acetate (manufactured by Daicel Corporation) were added. The mixture was stirred and heated to 130°C for approximately 4 hours. The disappearance of the NCO peak at 2250 cm⁻¹ was confirmed by FT-IR. Based on the confirmation of the NCO peak disappearance, this was considered the endpoint of the reaction. The reactants were cooled to room temperature and filtered through a 100-mesh filter to obtain elastomer 2 (50% by mass of non-volatile components) with an imine structure, a urethane structure, and a polybutadiene structure. The number average molecular weight was 13700. [Manufacturing Example 3. Manufacturing of Elastomer 3]

[0185] In a reaction vessel, 80 g of polycarbonate diol (number average molecular weight: approximately 1000, hydroxyl equivalent: 500 g / eq., non-volatile components: 100%, manufactured by Kuraray, Inc., "C-1015N") and 0.01 g of dibutyltin dilaurate were uniformly dissolved in 37.6 g of diethylene glycol monoethyl ether acetate (manufactured by Daicel, Inc., "Ethyl diglycol Acetate"). The mixture was then heated to 50°C, and while stirring, 27.8 g of toluene-2,4-diisocyanate (isocyanate equivalent: 87.08) was added, and the reaction was carried out for approximately 3 hours. After cooling the reactants to room temperature, 14.3 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent: 161.1 g / eq.), 0.12 g of triethylenediamine, and 84.0 g of diethylene glycol monoethyl ether acetate ("Ethyl diglycol Acetate" manufactured by Daicel Inc.) were added. The mixture was stirred and heated to 130°C for approximately 4 hours. The disappearance of the NCO peak at 2250 cm⁻¹ was confirmed by FT-IR. Based on the confirmation of the NCO peak disappearance, this was considered the endpoint of the reaction. The reactants were cooled to room temperature and filtered through a 100-mesh filter cloth to obtain elastomer 3 (50% by mass of non-volatile components) with an imine structure, a urethane structure, and a polycarbonate structure. The number average molecular weight was 8500. [Example 1]

[0186] While stirring, 2 parts of liquid chelate epoxy resin ("EP-49-10P" manufactured by ADEKA Corporation, epoxy equivalent 240 g / eq., chelate modified mass (phosphoric acid modified mass) 1.0 mass%), 4 parts of liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq.) and 3 parts of bixylenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 185 g / eq.) were heated and dissolved in 10 parts of MEK. After cooling to room temperature, 16 parts of elastomer 1 (50% by mass of non-volatile components), 10 parts of a phenolic curing agent with a triazine skeleton and phenolic structure (DIC Corporation "LA-3018-50P", active group equivalent of approximately 151 g / eq., 50% solids in a 2-methoxypropanol solution), 1 part of an imidazole curing accelerator (Shikoku Chemical Industry Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazolium, 5% by mass of MEK solution), 75 parts of inorganic filler 1, and 10 parts of MEK were mixed, uniformly dispersed using a high-speed rotary mixer, and then filtered through a cartridge filter (ROKITECHNO Corporation "SHP020") to produce a resin varnish. [Example 2]

[0187] The amount of chelated epoxy resin (ADEKA AG, "EP-49-10P", epoxy equivalent 240 g / eq.) was changed to 1.5 parts, and the amount of elastomer 1 (50% by mass of non-volatile components) was changed to 18 parts. Except for the above, the operation was carried out in the same manner as in Example 1 to manufacture the resin varnish. [Example 3]

[0188] The amount of chelated epoxy resin (ADEKA AG, "EP-49-10P", epoxy equivalent 240 g / eq.) was changed to 0.7 parts, and the amount of elastomer 1 (50% by mass of non-volatile components) was changed to 19 parts. Except for the above, the operation was carried out in the same manner as in Example 1 to manufacture the resin varnish. [Example 4]

[0189] The amount of chelated epoxy resin (ADEKA AG, "EP-49-10P", epoxy equivalent 240 g / eq.) was changed to 3 parts, and the amount of elastomer 1 (50% by mass of non-volatile components) was changed to 14 parts. Except for the above, the operation was carried out in the same manner as in Example 1 to manufacture the resin varnish. [Example 5]

[0190] The amount of chelated epoxy resin (ADEKA AG, "EP-49-10P", epoxy equivalent 240 g / eq.) was changed to 4 parts, and the amount of elastomer 1 (50% by mass of non-volatile components) was changed to 12 parts. Except for the above, the operation was carried out in the same manner as in Example 1 to manufacture the resin varnish. [Example 6]

[0191] The chelate-type epoxy resin (ADEKA AG "EP-49-10P", epoxy equivalent 240 g / eq.) was replaced with a liquid chelate-modified epoxy resin (ADEKA AG "EP-49-10P2", epoxy equivalent 300 g / eq., chelate modification mass (phosphoric acid modification mass) 1.5% by mass). Except for the above, the operation was the same as in Example 1 to manufacture the resin varnish. [Example 7]

[0192] The chelate-type epoxy resin (ADEKA AG "EP-49-10P", epoxy equivalent 240 g / eq.) was replaced with a liquid chelate-type epoxy resin (ADEKA AG "EP-49-23", epoxy equivalent 175 g / eq.). Except for the above, the operation was the same as in Example 1 to manufacture the resin varnish. [Example 8]

[0193] Except for using 75 parts of inorganic filler material 2 instead of 75 parts of inorganic filler material 1, the operation was the same as in Example 1 to manufacture the resin varnish. [Example 9]

[0194] Except for using 16 parts of elastomer 2 (50% by mass of non-volatile components) instead of 16 parts of elastomer 1 (50% by mass of non-volatile components), the operation was the same as in Example 1 to manufacture the resin varnish. [Example 10]

[0195] Except for using 16 parts of elastomer 3 (50% by mass of non-volatile components) instead of 16 parts of elastomer 1 (50% by mass of non-volatile components), the operation was the same as in Example 1 to manufacture the resin varnish. [Example 11]

[0196] Except for replacing 16 parts of elastomer 1 (50% by mass of non-volatile component) with 8 parts of hydroxyl-containing acrylic polymer (ARUFON UH-2000 manufactured by Toa Synthetic Co., Ltd., weight average molecular weight 11000), the resin varnish was manufactured in the same manner as in Example 1. [Example 12]

[0197] Except for replacing 10 parts of a phenolic varnish resin (DIC AG "TD-2090-60M", hydroxyl equivalent approximately 105 g / eq., 60% solids MEK solution) with a triazine skeleton and phenolic structure (DIC AG "LA-3018-50P", active group equivalent approximately 151 g / eq., 50% solids 2-methoxypropanol solution), the resin varnish was manufactured in the same manner as in Example 1. [Example 13]

[0198] Except for replacing 10 parts of a phenolic curing agent with a triazine skeleton and phenolic structure (DIC Corporation's "LA-3018-50P", active group equivalent of approximately 151 g / eq., 2-methoxypropanol solution with 50% solids) with 10 parts of naphthylphenol resin (Nippon Steel Chemical Materials Co., Ltd. "SN485", hydroxyl equivalent of approximately 215 g / eq.) with 60% solids, the operation was the same as in Example 1 to manufacture the resin varnish. [Example 14]

[0199] The resin varnish was prepared in the same manner as in Example 1, except that 10 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC AG, with an active group equivalent of approximately 223 g / eq. and a solid content of 65% by mass in toluene solution) was used instead of 10 parts of a phenolic curing agent having a triazine skeleton and phenolic structure (“LA-3018-50P” manufactured by DIC AG, with an active group equivalent of approximately 151 g / eq. and a solid content of 50% in 2-methoxypropanol solution). [Comparative Example 1]

[0200] Except for the absence of chelated epoxy resin (ADEKA AG "EP-49-10P", epoxy equivalent 240 g / eq.), the resin varnish was prepared in the same manner as in Example 1. [Comparative Example 2]

[0201] No chelate-type epoxy resin (ADEKA Co., Ltd. "EP-49-10P", epoxy equivalent 240 g / eq.) was used. Furthermore, the amount of liquid epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd. "ZX1059", a 1:1 mixture of bisphenol A and bisphenol F epoxy resins (mass ratio), epoxy equivalent: 169 g / eq.) was changed to 6 parts. Except for the above, the operation was the same as in Example 1 to manufacture the resin varnish. [Comparative Example 3]

[0202] No chelate-type epoxy resin (ADEKA AG "EP-49-10P", epoxy equivalent 240 g / eq.) was used. Furthermore, the amount of inorganic filler 1 was changed to 82 parts. Furthermore, the amount of a phenolic curing agent having a triazine skeleton and phenolic structure (DIC AG "LA-3018-50P", active group equivalent approximately 151 g / eq., 50% solids in a 2-methoxypropanol solution) was changed to 18 parts. Except for the above, the operation was the same as in Example 1 to manufacture the resin varnish. [Comparative Example 4]

[0203] No chelate-type epoxy resin (ADEKA Corporation "EP-49-10P", epoxy equivalent 240 g / eq.) was used. Furthermore, the amount of liquid epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd. "ZX1059", a 1:1 mixture of bisphenol A and bisphenol F epoxy resins (mass ratio), epoxy equivalent: 169 g / eq.) was changed to 6 parts. Then, 0.3 parts of a triazine-functionalized silane coupling agent (Shikoku Chemical Co., Ltd. "VD-5", 2,4-diamino-6-triethoxysilane triazine) was added to the resin varnish as an adhesion promoter. Except for the above, the resin varnish was manufactured in the same manner as in Example 1. [Manufacturing of Resin Sheets]

[0204] As a support, a polyethylene terephthalate film (LUMIRROR R80, Toray Industries, Inc., 38 μm thick, softening point 130°C) was prepared after being released by an alkyd resin release agent (AL-5, manufactured by Lintec Corporation). The resin varnish manufactured in the examples and comparative examples was applied to this support using a die coater at a drying resin composition layer thickness of 50 μm. The coating was dried at 85°C to 100°C for 4 minutes to obtain a resin sheet. [Evaluation of Copper Foil Adhesion Strength] <Substrate Treatment of Copper Clad Laminate>

[0205] A double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic Corporation "R-1766") was prepared on a glass cloth substrate with copper foil on the surface. Both sides were roughened by etching with a copper etching depth of 2 μm using a micro-etching agent (MEC Corporation "CZ8101"). The resulting copper-clad laminate is sometimes referred to as a "roughened copper-clad laminate". <Lamination of Resin Sheets>

[0206] The resin sheets manufactured in the examples and comparative examples were deposited on one side of the roughened copper-clad laminate using a batch vacuum pressure laminator (Nikko-Materials AG, 2-stage stacking laminator "CVP700") in a manner that bonded the resin composition layer to the roughened copper-clad laminate. The deposition was performed by depressurizing the pressure for 30 seconds to below 13 hPa, followed by pressing at 100°C and 0.74 MPa for 30 seconds. <Substrate treatment of copper foil>

[0207] Copper foil (electrolytic copper foil "3EC-III" manufactured by Mitsui Metals Mining Co., Ltd., 35 μm thick) was immersed in a micro-etching agent ("MECetchBOND CZ-8100" manufactured by MEC Corporation) to roughen the glossy surface of the copper foil (etching 1 μm). <Lamination and Hardening of Copper Foil>

[0208] A support for a resin sheet laminated to a roughened copper-clad laminate was peeled off to expose the resin composition layer. The resin composition layer and copper foil were laminated by bonding the roughened glossy surface to the resin composition layer. The lamination was performed by: depressurizing for 30 seconds to achieve a pressure below 13 hPa, followed by pressing at 100°C and 0.74 MPa for 30 seconds. Next, the resin composition layer was smoothed by hot pressing at 100°C and 0.5 MPa for 60 seconds under atmospheric pressure. Then, the resin composition was cured at 100°C for 30 minutes, followed by 190°C for 90 minutes, thereby obtaining a sample with a layer structure of "roughened copper-clad laminate / cured resin composition layer / copper foil". <Determination and evaluation of the peel strength of the copper foil>

[0209] A cut is made on the copper foil, enclosing a portion 10 mm wide and 100 mm long. One end of this portion is peeled off and clamped with a jig (AUTOCOM type testing machine "AC-50C-SL" manufactured by TSE Corporation). The load (kgf / cm) when peeling 20 mm vertically at a speed of 50 mm / min at room temperature is measured. The peel strength, which is the copper foil adhesion strength, is then determined. [Evaluation of Si adhesion strength] <Lamination and hardening on silicon wafers>

[0210] The resin sheets manufactured in the examples and comparative examples were deposited on one side of a 12-inch silicon wafer (775 μm thick) using a batch vacuum pressure laminator (Nikko-MaterialS, Inc., 2-stage stacking laminator "CVP700") to bond the resin composition layer to the silicon wafer. The deposition was performed by depressurizing for 30 seconds to bring the pressure down to below 13 hPa, and then pressing at 100°C and 0.74 MPa for 30 seconds. After deposition, the support for the resin sheet was peeled off. The resin composition was cured at 100°C for 30 minutes, followed by 190°C for 90 minutes, thereby obtaining a laminate consisting of a "silicon wafer / cured resin composition layer". <Preparation of Test Sheets>

[0211] Cut 1cm cubes from the obtained laminate and place them on an 11.4cm cube (P / N901450) of ceramic pad with epoxy adhesive, with the hardened layer facing upwards. Then, fix the studpin (nail-shaped mold; adhesive surface diameter 2.7 mm, P / N901106) to the hardened layer with epoxy adhesive, and heat at 150°C for 1 hour to bond the studpin to the hardened layer. <Stud Pull Test>

[0212] Using a column bolt traction testing machine (ROMULUS, Quad Group Inc.), the column bolt pin was stretched at a speed of 2 kgf / s in a direction perpendicular to the main surface of the hardened layer. The load value (kgf / cm2) at which the hardened layer peeled off was measured as the Si bond strength. [Evaluation of Warpage]

[0213] The resin sheets manufactured in the examples and comparative examples were deposited on the entire single side of a 12-inch silicon wafer (775 μm thick) using a batch vacuum pressure laminator (Nikko-MaterialS, Inc., 2-stage stacking laminator "CVP700") to bond the resin composition layer to the silicon wafer. The support of the resin sheet was peeled off to expose the resin composition layer, and a resin sheet was then deposited on the surface of the resin composition layer in the same manner, and the support was peeled off. By the aforementioned deposition, two resin composition layers (total thickness 100 μm) were formed on a single side of the 12-inch silicon wafer. Furthermore, the deposition was performed under the same conditions as described above in the [Evaluation of Si Adhesion Strength].

[0214] The resin composition layer was hardened by heating in an oven at 100°C for 30 minutes, followed by 190°C for 90 minutes, to obtain a laminate consisting of a "silicon wafer / hardened resin composition layer". The end of the obtained laminate was pressed against a horizontal mesa. The distance between the wafer end (opposite to the pressed end) and the mesa was measured as the warpage. Warpage was evaluated according to the following criteria: Warpage evaluation criteria: "○": Warpage ≥ 0 mm and ≤ 1.5 mm (1500 μm); "×": Warpage > 1.5 mm. [Determination of elastic modulus]

[0215] The resin sheets manufactured in the examples and comparative examples were heat-cured at 190°C for 90 minutes, and the support was peeled off to obtain sheet-like cured products. Tensile tests were performed on the cured products using a Tensilon universal testing machine (manufactured by A&D Corporation) according to Japanese Industrial Standard (JIS K7127), and the elastic modulus (tensile modulus) of the cured products at room temperature was measured. [Melt Viscosity Measurement]

[0216] A resin composition layer was obtained by peeling the support from the resin sheet manufactured in the Examples and Comparative Examples. Test particles (18 mm in diameter, 1.0 g to 1.1 g) were manufactured by compressing the resin composition layer using a mold. The minimum melt viscosity was then determined using a dynamic viscoelasticity measuring apparatus (UBM Rheosol-G3000, UBM Inc.). Specifically, for 1 g of test particles, a parallel plate with a diameter of 18 mm was used, and the temperature was increased from an initial temperature of 60°C to 200°C while measuring the dynamic viscoelastic modulus to determine its minimum value. The measurement conditions were set as follows: heating rate 5°C / min, temperature interval 2.5°C, vibration frequency 1 Hz, and deformation 5 degrees. [Results]

[0217] The results of the above-described examples and comparative examples are shown in the table below. In the table below, the abbreviations have the following meanings; (B) Content: (B) Content of inorganic filler material; Active group ratio: (D) Number of active groups of the curing agent when (A) The number of epoxy groups of the epoxy resin is set to 1.

[0218]

[0219] [Simplified Explanation of the Diagram]

[0013] [Figure 1] is a cross-sectional view showing a fan-out type WLP as an example of a semiconductor wafer package related to one embodiment of the present invention.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, and (C) an elastomer, wherein (A) the epoxy resin comprises: (A-1) an epoxy resin containing epoxy groups and having a chelate-forming ability, the chelate-forming ability comprising at least one atom selected from the group consisting of oxygen and nitrogen; the amount of (A) component relative to 100% by mass of the resin component of the resin composition is 10% to 70% by mass; the amount of (B) component relative to 100% by mass of the non-volatile component of the resin composition is 40% to 95% by mass; the amount of (C) component relative to 100% by mass of the non-volatile component of the resin composition is 1% to 20% by mass; and (C) the elastomer is selected from the group consisting of resins containing a polybutadiene structure and resins having an intramolecular amide structure, a urethane structure, and a polycarbonate structure.

2. The resin composition as claimed in claim 1, wherein, The chelate of component (A-1) is modified to 0.3% to 10% by mass.

3. The resin composition as claimed in claim 1, wherein, The ratio of the mass of component (A-1) W(A-1) to the mass of component (C) W(C) is 0.01 to 1.

0.

4. The resin composition as claimed in claim 1, wherein, (C) Component has a number average molecular weight of over 1000.

5. The resin composition as claimed in claim 1, wherein, It further includes (D) a hardener.

6. The resin composition as claimed in claim 1, wherein, It further contains (E) a hardening accelerator.

7. The resin composition as requested in item 1 is for use as a sealing layer.

8. A cured material, which is a cured material of the resin composition of any one of claims 1 to 7.

9. A resin sheet comprising: a support and a resin composition layer formed on the support, comprising any one of claims 1 to 7.

10. A circuit board comprising a cured material containing a resin composition as claimed in any one of claims 1 to 7.

11. A semiconductor wafer package comprising a cured material containing a resin composition as described in any one of claims 1 to 7.

12. A semiconductor device comprising a circuit board as claimed in claim 10 or a semiconductor wafer package as claimed in claim 11.

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