resin composition

Abstract

To provide a resin composition that can give a cured product to resist warping and show good adhesion to a conductor layer.SOLUTION: A resin composition comprises (A) epoxy resin, (B) inorganic filler, and (C) elastomers, the (A) epoxy resin including (A-1) epoxy resin having an epoxy group and a chelate forming capacity.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin composition, and to a cured product, resin sheet, circuit board, semiconductor chip package, and semiconductor device using the resin composition. [Background technology]

[0002] In recent years, demand for small, high-performance electronic devices such as smartphones and tablet devices has increased, and consequently, there is a growing need for even higher performance encapsulants for semiconductor chip packages used in these small electronic devices. One such encapsulant known to be formed by curing a resin composition is one such example. On the other hand, as technologies for applications different from sealing materials, there are the technologies described in Patent Documents 1 and 2. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2018-80221 [Patent Document 2] Patent No. 5491276 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Resin compositions used as encapsulants generally contain inorganic fillers for purposes such as improving insulation and sealing properties. Cured products of resin compositions containing such inorganic fillers tend to exhibit significant warping.

[0005] If the cured product contains a fibrous base material, such as a prepreg, the fibrous base material can increase the overall rigidity of the cured product and reduce thermal expansion, thus suppressing warping. However, since encapsulants typically do not contain a fibrous base material, suppressing warping has been difficult.

[0006] Therefore, the inventors attempted to suppress warping by lowering the elastic modulus of the cured resin composition. Specifically, they attempted to suppress warping by using a resin composition containing an elastomer to lower the elastic modulus of the cured product. As a result, warping suppression was achieved. However, the cured product of the resin composition containing the elastomer had poor adhesion to the conductive layer.

[0007] Therefore, the inventors conducted further studies and attempted to improve adhesion by using an adhesion promoter in combination with the elastomer. However, while the adhesion improved when the adhesion promoter was used, the warping increased. Consequently, it was difficult to achieve both warping suppression and improved adhesion with conventional sealing materials.

[0008] The present invention was devised in view of the above-mentioned problems, and aims to provide a resin composition that can produce a cured product with excellent warp suppression and adhesion to a conductor layer; a cured product of the resin composition; and a resin sheet, circuit board, semiconductor chip package, and semiconductor device using the resin composition. [Means for solving the problem]

[0009] The inventors diligently studied to solve the above-mentioned problems. As a result, the inventors found that the above-mentioned problems can be solved by a resin composition comprising (A) epoxy resin, (B) inorganic filler, and (C) elastomer, wherein (A) epoxy resin contains (A-1) epoxy groups and a structure having chelating ability, and thus completed the present invention. In other words, the present invention includes the following:

[0010] [1] (A) epoxy resin, (B) inorganic filler, and (C) elastomer, (A) A resin composition comprising an epoxy resin containing (A-1) an epoxy resin having an epoxy group and a structure having chelating ability. [2] The resin composition according to [1], wherein the amount of chelation modification of component (A-1) is 0.3% by mass to 10% by mass. 〔3〕The resin composition according to 〔1〕or 〔2〕, wherein the ratio W(A-1) / W(C) of the mass W(A-1) of the (A-1) component to the mass W(C) of the (C) component is 0.01 to 1.0. 〔4〕The resin composition according to any one of 〔1〕to 〔3〕, wherein the amount of the (B) component is 40% by mass or more based on 100% by mass of the non-volatile components of the resin composition. 〔5〕The resin composition according to any one of 〔1〕to 〔4〕, wherein the (C) component has a number average molecular weight of 1000 or more. 〔6〕The resin composition according to any one of 〔1〕to 〔5〕, further comprising a (D) curing agent. 〔7〕The resin composition according to any one of 〔1〕to 〔6〕, further comprising an (E) curing accelerator. 〔8〕The resin composition according to any one of 〔1〕to 〔7〕, which is for a sealing layer. 〔9〕A cured product of the resin composition according to any one of 〔1〕to 〔8〕. 〔10〕A resin sheet comprising a support and a resin composition layer formed on the support and containing the resin composition according to any one of 〔1〕to 〔8〕. 〔11〕A circuit board containing a cured product of the resin composition according to any one of 〔1〕to 〔8〕. 〔12〕A semiconductor chip package containing a cured product of the resin composition according to any one of 〔1〕to 〔8〕. 〔13〕A semiconductor device comprising the circuit board according to 〔11〕or the semiconductor chip package according to 〔12〕.

Advantages of the Invention

[0011] According to the present invention, there are provided a resin composition capable of obtaining a cured product excellent in warpage suppression and adhesion to a conductor layer; a cured product of the resin composition; and a resin sheet, a circuit board, a semiconductor chip package, and a semiconductor device using the resin composition.

Brief Description of the Drawings

[0012] [Figure 1]FIG. 1 is a cross-sectional view schematically showing a Fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention. [Embodiments for Carrying out the Invention]

[0013] Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented without departing from the scope of the claims and their equivalents.

[0014] [1. Overview of Resin Composition] The resin composition according to an embodiment of the present invention contains, in combination, (A) an epoxy resin, (B) an inorganic filler, and (C) an elastomer. And, the (A) epoxy resin contains an epoxy resin having a structure containing an epoxy group and a chelating ability (A-1). In the following description, the “epoxy resin having a structure containing an epoxy group and a chelating ability (A-1)” may be referred to as “(A-1) chelate type epoxy resin”. Also, in the following description, the “structure having a chelating ability” may be referred to as “chelating ability structure”.

[0015] The resin composition according to the present embodiment can obtain a cured product by thermosetting. And, the obtained cured product can be excellent in suppressing warpage and adhesion to the conductor layer. Also, the cured product of the resin composition according to the present embodiment can usually be excellent in adhesion to silicon. Furthermore, the resin composition according to the present embodiment preferably has a low minimum melt viscosity, and preferably obtains a cured product having a small tensile elastic modulus.

[0016] The resin composition according to the present embodiment may further contain an arbitrary component in combination with the above-described components. For example, the resin composition may contain (D) a curing agent, (E) a curing accelerator, and the like.

[0017] [2. (A) Epoxy Resin] The resin composition according to this embodiment includes (A) epoxy resin as component (A). (A) epoxy resin is a curable resin having epoxy groups.

[0018] The epoxy resin (A) according to this embodiment includes a chelate-type epoxy resin (A-1) as component (A-1). The chelate-type epoxy resin (A-1) contains epoxy groups and a chelating structure.

[0019] A chelating structure represents a structure that has the ability to form chelates. This chelating structure usually contains at least one atom selected from the group consisting of oxygen and nitrogen. In the following description, atoms selected from the group consisting of oxygen and nitrogen may be referred to as "specific atoms." A single chelating structure usually contains multiple specific atoms. Since the multiple specific atoms are generally not directly bonded, there are molecular chains that connect these specific atoms. That is, specific atoms are usually connected to each other by molecular chains. Here, the atoms included in the molecular chains do not include oxygen atoms and nitrogen atoms. The number of atoms in the molecular chains is usually 1 or more, preferably 2 or more, and preferably 6 or less. Here, the number of atoms in the molecular chains that connect the specific atoms represents the minimum number of atoms between the specific atoms connected by the molecular chains. Therefore, even if branched chains are bonded to the molecular chain, the number of atoms included in those branched chains is not included in the number of atoms in the molecular chain. Therefore, the chelating structure may preferably be a structure containing adjacent specific atoms via 1 to 6 atoms, more preferably 2 to 6 atoms. In this chelating structure, some or all of the specific atoms may function as coordination atoms.

[0020] The chelating structure preferably contains an oxygen atom as a specific atom. It is more preferable that at least one of the oxygen atoms designated as specific atoms originates from a hydroxyl group. That is, it is more preferable that the chelating structure contains a hydroxyl group, and that the oxygen atom contained in that hydroxyl group is the specific atom of the chelating structure. Furthermore, it is more preferable that at least one of the oxygen atoms designated as specific atoms originates from a carbonyl group. That is, it is more preferable that the chelating structure contains a carbonyl group, and that the oxygen atom contained in that carbonyl group is the specific atom of the chelating structure.

[0021] When a chelate 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 structure are adjacent to each other via two atoms. The chelate structure may contain only one set of two oxygen atoms adjacent to each other via two atoms as described above, or it may contain two or more such sets.

[0022] Chelating structures typically contain carbon and hydrogen atoms in combination with specific atoms. Furthermore, chelating structures may also contain any heteroatoms other than oxygen and nitrogen atoms. Preferred heteroatoms in chelating structures include phosphorus and sulfur atoms. The number of heteroatoms may be one or more.

[0023] Specific examples of preferred chelating structures include carboxyl groups and phosphate groups. Of these, phosphate groups are more preferred. The chelating structure may be present in the basic skeleton, side chains, or terminals of the (A-1) chelate-type epoxy resin. The (A-1) chelate-type epoxy resin may contain one type of chelating structure or two or more types. Furthermore, the number of chelating structures contained in one molecule of the (A-1) chelate-type epoxy resin may be one or two or more.

[0024] (A-1) The number of epoxy groups contained in one molecule of the chelate-type epoxy resin may be one or two or more.

[0025] (A-1) Chelate epoxy resins preferably contain aromatic structures in their molecules. An aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocyclics. When using a (A-1) chelate epoxy resin containing an aromatic ring structure, the heat resistance of the cured resin composition can be improved.

[0026] (A-1) Chelate epoxy resins may include structures obtained by reacting an epoxy resin that does not contain a chelating structure with a compound that contains a chelating structure. For example, (A-1) chelate epoxy resins containing phosphate groups may include structures obtained by reacting an epoxy resin that does not contain a chelating structure with phosphates. Examples of phosphates include phosphate (H3PO4), phosphonic acid (H3PO3), magnetophosphate (H3PO2), diphosphate (H4P2O7), and polyphosphates such as triphosphate.

[0027] (A-1) Chelate epoxy resins can be produced, for example, by a method that includes glycidyl etherification of the hydroxyl group of a compound having a phenolic or alcoholic hydroxyl group and a chelating structure. Alternatively, (A-1) chelate epoxy resins can be produced, for example, by a method that includes reacting an epoxy resin that does not contain a chelating structure with a compound that contains a chelating structure. Specifically, (A-1) chelate epoxy resins containing phosphate groups can be produced by the method described in International Publication No. 2021 / 039380.

[0028] In a method for producing (A-1) chelated epoxy resin, which involves reacting an epoxy resin that does not contain a chelate structure with a compound that contains a chelate structure, the compound containing the chelate structure usually reacts with the epoxy groups of the epoxy resin to obtain the (A-1) chelated epoxy resin. In this case, the amount of the compound containing the chelate structure that reacts is expressed as the amount of chelate modification. Specifically, the amount of chelate modification is expressed as the ratio of the compound containing the chelate structure that reacted with the epoxy resin to 100% by mass of the epoxy resin that does not contain a chelate structure. The amount of chelate modification is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.8% by mass or 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 amount of chelate modification is within the above range, the adhesion of the cured resin composition can be effectively improved.

[0029] (A-1) Commercially available chelate epoxy resins may be used. Examples of commercially available (A-1) chelate epoxy resins include "EP-49-10P" and "EP-49-10P2" from ADEKA Corporation (both reaction products of bisphenol A type epoxy resin and phosphoric acid); and "EP-49-23" from ADEKA Corporation.

[0030] (A-1) Chelate epoxy resins may be used individually or in combination of two or more types.

[0031] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The (A-1) chelate-type epoxy resin included in the resin composition may be liquid epoxy resin only, solid epoxy resin only, 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.

[0032] (A-1) The epoxy equivalent of the chelate-type epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 3,000 g / eq., even more preferably 80 g / eq. to 2,000 g / eq., and particularly preferably 110 g / eq. to 1,000 g / eq. The epoxy equivalent represents the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0033] (A-1) The weight-average molecular weight (Mw) of the chelate-type epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The number-average molecular weight of the chelate-type epoxy resin is usually less than 5,000, preferably less than 3,000. The weight-average molecular weight and number-average molecular weight of the resin can be measured as polystyrene equivalent values ​​by gel permeation chromatography (GPC).

[0034] The amount of (A-1) chelate-type 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, based on 100% by mass of the nonvolatile components of the resin composition. When the amount of (A-1) chelate-type epoxy resin is within the above range, adhesion can be effectively improved while suppressing warping, and furthermore, the minimum melt viscosity can usually be effectively lowered.

[0035] The amount of (A-1) chelate-type 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, based on 100% by mass of the resin components of the resin composition. Unless otherwise specified, the resin components of the resin composition refer to the non-volatile components of the resin composition excluding (B) inorganic fillers. When the amount of (A-1) chelate-type epoxy resin is within the above range, adhesion can be effectively improved while suppressing warping, and furthermore, the minimum melt viscosity can usually be effectively lowered.

[0036] (A) The mass of the chelate-type epoxy resin (A-1) relative to 100% by mass of the total epoxy resin 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 the chelate-type epoxy resin (A-1) is within the above range, adhesion can be effectively improved while suppressing warping, and furthermore, the minimum melt viscosity can usually be effectively lowered.

[0037] The ratio W(A-1) / W(C) of the mass of the (A-1) chelate-type epoxy resin and the mass of the (C) elastomer in the resin composition is preferably within a specific range. Specifically, the ratio W(A-1) / W(C) is preferably 0.01 or higher, more preferably 0.02 or higher, particularly preferably 0.04 or higher, preferably 1.0 or lower, more preferably 0.8 or lower, and particularly preferably 0.7 or lower. When the ratio W(A-1) / W(C) is within the above range, adhesion can be effectively improved while suppressing warping, and furthermore, the minimum melt viscosity can usually be effectively lowered.

[0038] (A) The epoxy resin may be combined with (A-1) the chelate-type epoxy resin and (A-2) contain an epoxy resin other than (A-1) the chelate-type epoxy resin as component (A-2). In the following description, "(A-2) the epoxy resin other than (A-1) the chelate-type epoxy resin" may be referred to as "(A-2) any epoxy resin".

[0039] (A-2) Examples of any epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiroring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthaleimidine type epoxy resin, etc. (A-2) Any epoxy resin may be used alone or in combination of two or more types.

[0040] (A-2) From the viewpoint of obtaining a cured product with excellent heat resistance, it is preferable that the epoxy resin includes an epoxy resin containing an aromatic structure. Examples of (A-2) epoxy resins containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bisquilenol type epoxy resin, glycidylamine type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy resin having a butadiene structure having an aromatic structure, alicyclic epoxy resin having an aromatic structure, heterocyclic epoxy resin, spiroring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, and tetraphenylethane type epoxy resin having an aromatic structure.

[0041] (A-2) Preferably, the epoxy resin contains an epoxy resin having two or more epoxy groups in one molecule. (A-2) The proportion of the epoxy resin having two or more epoxy groups in one molecule, relative to 100% by mass of the nonvolatile component of the epoxy resin, is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0042] (A-2) Any epoxy resin may be liquid epoxy resin only, solid epoxy resin only, or a combination of liquid epoxy resin and solid epoxy resin.

[0043] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred. (A-2) Examples of preferred liquid epoxy resins that can be used as any epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resins having a butadiene structure.

[0044] (A-2)Specific examples of liquid epoxy resins that can be used as any epoxy resin include: DIC Corporation's "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical Corporation's "828US", "828EL", "jER828EL", "825", "Epicote 828EL" (bisphenol A-type epoxy resin); Mitsubishi Chemical Corporation's "jER807", "1750" (bisphenol F-type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenol novolac-type epoxy resin); Mitsubishi Chemical Corporation's "630", "630LSD", "604" (glycidylamine-type epoxy resin); and ADEKA Corporation's "ED-5 Examples include "23T" (glycyrol-type epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resins) from ADEKA Corporation; "EP-4088S" (dicyclopentadiene-type epoxy resin) from ADEKA Corporation; "ZX-1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) from Nippon Steel Chemical & Material Co., Ltd.; "PB-3600" from Daicel Corporation; "JP-100" and "JP-200" (epoxy resins with a butadiene structure) from Nippon Soda Co., Ltd.; and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) from Nippon Steel Chemical & Material Co., Ltd. These can be used individually or in combination of two or more types.

[0045] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred. (A-2) Preferred solid epoxy resins that can be used as any epoxy resin include, for example, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, and phenolphthaleimidine type epoxy resin.

[0046] (A-2)Specific examples of solid epoxy resins that can be used as any epoxy resin include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin); DIC's "N-690" (cresol novolac-type epoxy resin); DIC's "N-695" (cresol novolac-type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin). Xylionic resin; DIC Corporation's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) Resins); "ESN475V" and "ESN4100V" (naphthalene-type epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bixylenol-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Examples include "YX8800" (anthracene-type epoxy resin); "YX7700" (phenol aralkyl-type epoxy resin) from Mitsubishi Chemical Corporation; "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) from Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) from Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) from Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthaleimidine-type epoxy resin) from Nippon Kayaku Co., Ltd.These may be used individually or in combination of two or more types.

[0047] (A-2) The range of epoxy equivalents for any epoxy resin may be the same as (A-1) the range of epoxy equivalents for chelate-type epoxy resins.

[0048] (A-2) The weight-average molecular weight and number-average molecular weight ranges of any epoxy resin may be the same as (A-1) the weight-average molecular weight and number-average molecular weight ranges of chelate-type epoxy resins.

[0049] (A) When liquid epoxy resin and solid epoxy resin are used in combination as the epoxy resin, their mass ratio (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.

[0050] 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, based on 100% by mass of the nonvolatile components of the resin composition. When the amount of epoxy resin (A) is within the above range, the effects of suppressing warping and improving adhesion can be significantly obtained, and furthermore, the minimum melt viscosity can usually be effectively lowered.

[0051] The amount of epoxy resin (A) 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, based on 100% by mass of the resin components of the resin composition. When the amount of epoxy resin (A) is within the above range, the effects of suppressing warping and improving adhesion can be significantly obtained, and furthermore, the minimum melt viscosity can usually be effectively lowered.

[0052] [3.(B) Inorganic filler] The resin composition according to this embodiment includes (B) an inorganic filler as component (B). The inorganic filler (B) is usually included in the resin composition in particulate form.

[0053] (B) Inorganic compounds are used as the material for the inorganic filler. (B) Examples of materials for the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica and alumina are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred as silica. (B) The inorganic filler may be used alone or in combination of two or more types.

[0054] (B) Examples of commercially available inorganic fillers include "UFP-30" from Denka Chemical Industries, Ltd.; "SP60-05" and "SP507-05" from Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" from Admatex Corporation; "UFP-30" from Denka Corporation; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; and "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", and "SC2050-SXF" from Admatex Corporation.

[0055] (B) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0056] (B) The average particle size of the inorganic filler can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the average particle size can be measured by taking the median diameter as the average particle size. A sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them with ultrasound for 10 minutes. The sample can be measured using a laser diffraction-type particle size distribution analyzer with blue and red light source wavelengths, using a flow cell method to measure the volume-based particle size distribution of the inorganic filler, and the average particle size can be calculated as the median diameter from the obtained particle size distribution. An example of a laser diffraction-type particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0057] (B) The specific surface area of ​​the inorganic filler is preferably 1 m², from the viewpoint of significantly obtaining the desired effects of the present invention. 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 It must be 1 / g or more. There is no particular upper limit, but preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The value is less than / g. 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 Mountec) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0058] (B) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane 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 types may be used in any combination.

[0059] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy-type silane coupling agent), and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), all manufactured by Shin-Etsu Chemical Co., Ltd.

[0060] (B) From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler 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.

[0061] The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler should be 0.02 mg / m². 2 The above is preferred, and 0.1 mg / m² 2The above is more preferable, 0.2 mg / m 2 The above is even more preferable. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin composition, 1.0 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less is even more preferable.

[0062] (B) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0063] The amount of (B) inorganic filler in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less, based on 100% by mass of the non-volatile components of the resin composition. Generally, when the amount of the inorganic filler is large as described above, problems such as an increase in the minimum melt viscosity of the resin composition and a decrease in the adhesion of the cured product of the resin composition are likely to occur. In contrast, according to the resin composition according to the present embodiment, even when the inorganic filler is large as described above, the adhesion of the cured product can be improved, and more preferably, the minimum melt viscosity can be lowered. Therefore, when a large amount of (B) inorganic filler above the lower limit value is included, the advantages of the resin composition according to the present embodiment can be particularly effectively utilized. Further, when the amount of (B) inorganic filler is below the upper limit value, the effects of suppressing warping and improving adhesion can be significantly obtained, and usually, the minimum melt viscosity can be effectively lowered. <​​​​The resin composition according to this embodiment includes an elastomer (C) as component (C). This elastomer (C) does not include components (A) to (B) described above. The elastomer (C) is a flexible resin, preferably a resin that exhibits rubber elasticity when polymerized with a rubber-elastic resin or other components. As for rubber elasticity, for example, a resin that exhibits an elastic modulus of 1 GPa or less when subjected to a tensile test at a temperature of 25°C and a humidity of 40% RH in accordance with the Japanese Industrial Standard (JIS K7161). The elastomer (C) is usually an amorphous resin component that can be dissolved in an organic solvent. The elastomer (C) may be used alone or in combination of two or more types in any ratio. The elastomer (C) can lower the elastic modulus of the cured product of the resin composition.

[0065] (C) The elastomer is preferably high molecular weight. The number average molecular weight (Mn) of the (C) elastomer is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, and particularly preferably 5,000 or more. When the (C) elastomer has a high molecular weight as described above, the effects of suppressing warping and improving adhesion can be significantly obtained, and furthermore, the minimum melt viscosity can usually be effectively lowered. There is no particular upper limit to the number average molecular weight, but it is preferably 1,000,000 or less, more preferably 900,000 or less. The number average molecular weight (Mn) is the number average molecular weight on a polystyrene basis measured using GPC (gel permeation chromatography).

[0066] (C) The elastomer is preferably one or more selected from resins having a glass transition temperature (Tg) of 25°C or lower and resins that are liquid at 25°C or lower. The glass transition temperature of resins having a glass transition temperature (Tg) of 25°C or lower is preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but can usually be -15°C or higher. The resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or lower, more preferably a resin that is liquid at 15°C or lower. The glass transition temperature can be measured by DSC (Differential Scanning Calorimetry) at a heating rate of 5°C / min.

[0067] (C) The elastomer is preferably a resin having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkylene oxy, polyisoprene, polyisobutylene, polycarbonate, and polystyrene structures within its molecule. "(meth)acrylate" is a term that includes methacrylate and acrylate, as well as combinations thereof. These structures may be included in the main chain or side chain of the molecule of (C) the elastomer.

[0068] (C) Examples of elastomers include resins containing a polybutadiene structure. The polybutadiene structure may be included in the main chain or in the side chain. Furthermore, the polybutadiene structure may be partially or entirely hydrogenated. Resins containing a polybutadiene structure are sometimes called "polybutadiene resins". Specific examples of polybutadiene resins include Clay Valley's "Ricon 130MA8," "Ricon 130MA13," "Ricon 130MA20," "Ricon 131MA5," "Ricon 131MA10," "Ricon 131MA17," "Ricon 131MA20," and "Ricon 184MA6" (polybutadiene containing acid anhydride groups); Nippon Soda's "GQ-1000" (polybutadiene with hydroxyl and carboxyl groups), "G-1000," "G-2000," and "G-3000" (polybutadiene with hydroxyl groups at both ends), "GI-1000," "GI-2000," and "GI-3000" (hydrogenated polybutadiene with hydroxyl groups at both ends); and Nagase ChemteX's "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin). Furthermore, specific examples of polybutadiene resins include phenolic hydroxyl group-containing butadiene resins and polyimide resins having polybutadiene structures, urethane structures, and imide structures within the molecule. The polyimide resin can be produced as a linear polyimide resin (polyimide described in Japanese Patent Publication No. 2006-37083 and International Publication No. 2008 / 153208) using hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides as raw materials. The butadiene structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be found in Japanese Patent Publication No. 2006-37083 and International Publication No. 2008 / 153208, which are incorporated herein by reference.

[0069] (C) Examples of elastomers include resins containing a poly(meth)acrylate structure. Resins containing a poly(meth)acrylate structure are sometimes called "poly(meth)acrylic resins". Specific examples of poly(meth)acrylic resins include Teisan Resin manufactured by Nagase ChemteX Corporation; ME-2000, W-116.3, W-197C, KG-25, and KG-3000 manufactured by Negami Kogyo Co., Ltd.; and ARUFON UH-2000 manufactured by Toagosei Co., Ltd.

[0070] (C) Examples of elastomers include resins containing a polycarbonate structure. Resins containing a polycarbonate structure are sometimes called "polycarbonate resins". Specific examples of polycarbonate resins include "FPC0220" and "FPC2136" from Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) from Asahi Kasei Chemicals Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) from Kuraray Co., Ltd. Furthermore, specific examples of polycarbonate resins include polyimide resins having imide structures, urethane structures, and polycarbonate structures in their molecules. These polyimide resins can be manufactured as linear polyimide resins using hydroxyl-terminated polycarbonates, diisocyanate compounds, and tetrabasic acid anhydrides as raw materials. The content of the carbonate structure in the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be found in International Publication No. 2016 / 129541, which is incorporated herein by reference.

[0071] (C) Examples of elastomers include resins containing a polysiloxane structure. Resins containing a polysiloxane structure are sometimes called "siloxane resins". Specific examples of siloxane resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., as well as linear polyimides made from amine-terminated polysiloxanes and tetrabasic acid anhydrides (International Publication No. 2010 / 053185, Japanese Patent Publication No. 2002-12667 and Japanese Patent Publication No. 2000-319386, etc.).

[0072] (C) Examples of elastomers include resins containing a polyalkylene structure or a polyalkylene oxy structure. Resins containing a polyalkylene structure are sometimes called "alkylene resins." Resins containing a polyalkylene oxy structure are sometimes called "alkylene oxy resins." The polyalkylene oxy structure is preferably a polyalkylene oxy structure with 2 to 15 carbon atoms, more preferably a polyalkylene oxy structure with 3 to 10 carbon atoms, and particularly preferably a polyalkylene oxy structure with 5 to 6 carbon atoms. Specific examples of alkylene resins and alkylene oxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Co., Ltd.

[0073] (C) Examples of elastomers include resins containing a polyisoprene structure. Resins containing a polyisoprene structure are sometimes called "isoprene resins." Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

[0074] (C) Examples of elastomers include resins containing a polyisobutylene structure. Resins containing a polyisobutylene structure are sometimes called "isobutylene resins". Specific examples of isobutylene resins include Kaneka's "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer).

[0075] (C) Examples of elastomers include resins containing a polystyrene structure. Resins containing a polystyrene structure are sometimes called "polystyrene resins". Polystyrene resins may be copolymers that contain any repeating units different from the aforementioned styrene units in combination with styrene units, and may also be hydrogenated polystyrene resins. Examples of polystyrene resins include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-maleic anhydride copolymer, and the like. Specific examples of polystyrene resins include the hydrogenated styrene thermoplastic elastomers "H1041," "ToughTec H1043," "ToughTec P2000," and "ToughTec MP10" (manufactured by Asahi Kasei Corporation); the epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT501" and "CT310" (manufactured by Daicel Corporation); the modified styrene elastomer "Septon HG252" (manufactured by Kuraray Co., Ltd.) which has a hydroxyl group; the modified styrene elastomer "ToughTec N503M" which has a carboxyl group; the modified styrene elastomer "ToughTec N501" which has an amino group; the modified styrene elastomer "ToughTec M1913" (manufactured by Asahi Kasei Chemicals Corporation) which has an acid anhydride group; the unmodified styrene elastomer "Septon S8104" (manufactured by Kuraray Co., Ltd.); and the styrene-ethylene / butylene-styrene block copolymers "FG1924" (manufactured by Kraton) and "EF-40" (manufactured by Cray Valley).

[0076] Among those mentioned above, the (C) elastomer is more preferably a resin containing at least one structure selected from the group consisting of a polybutadiene structure, a polycarbonate structure, and a poly(meth)acrylate structure within its molecule. Furthermore, the (C) elastomer is particularly preferably a resin having a polybutadiene structure or a polycarbonate structure within its molecule. (C) elastomers having a polybutadiene structure or a polycarbonate structure generally have low compatibility with (A-1) chelate-type epoxy resins. Therefore, these (C) elastomers can microscopically separate from the (A-1) chelate-type epoxy resin and form minute domains with excellent flexibility. In the cured product of the resin composition, the flexibility of these domains is exhibited, which effectively reduces the elastic modulus of the cured product, thus particularly effectively suppressing warping without impairing adhesion.

[0077] (C) The elastomer may have functional groups that can react with (A) the epoxy resin. When (C) the elastomer reacts with (A) the epoxy resin, the mechanical strength of the cured resin composition can be increased. Functional groups that can react with (A) the epoxy resin include functional groups that appear upon heating. Functional groups that can react with (A) the epoxy resin may be one or more functional groups selected from the group consisting of hydroxyl groups, carboxyl groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, and urethane groups. Among these, hydroxyl groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, and urethane groups are preferred, hydroxyl groups, acid anhydride groups, phenolic hydroxyl groups, and epoxy groups are more preferred, and phenolic hydroxyl groups are particularly preferred. The number average molecular weight (Mn) of the (C) elastomer containing the functional groups is preferably 5,000 or more.

[0078] 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, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the nonvolatile components of the resin composition. When the amount of (C) elastomer is within the above range, the effects of suppressing warping and improving adhesion can be significantly obtained, and furthermore, the minimum melt viscosity can usually be effectively lowered.

[0079] The amount of (C) elastomer in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on 100% by mass of the resin components of the resin composition. When the amount of (C) elastomer is within the above range, the effects of suppressing warping and improving adhesion can be significantly obtained, and furthermore, the minimum melt viscosity can usually be effectively lowered.

[0080] [5. (D) Hardener] The resin composition according to this embodiment may further contain a curing agent (D) as an optional component in combination with the components (A) to (C) described above. This curing agent (D) does not include any of the components (A) to (C) described above. The curing agent (D) may have the function of curing the resin composition by reacting with the epoxy resin (A).

[0081] (D) Examples of curing agents include phenolic curing agents, naphthol curing agents, activated 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 activated ester curing agents are preferred, and phenolic curing agents and activated ester curing agents are particularly preferred. (D) A single curing agent may be used, or two or more may be used in combination.

[0082] From the viewpoint of heat resistance and water resistance, phenolic and naphthol-based curing agents are preferred if they have a novolac structure. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred.

[0083] Specific examples of phenol-based and naphthol-based curing agents include, for example, "MEH-7700," "MEH-7810," "MEH-7851," and "MEH-8000H" from Meiwa Kasei Co., Ltd.; "NHN," "CBN," and "GPH" from Nippon Kayaku Co., Ltd.; and "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-495V," and "SN-37" from Nippon Steel Chemical & Material Co., Ltd. Examples include "5", "SN-395", "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" from DIC Corporation, and "GDP-6115L", "GDP-6115H", "ELPC75" from Gun-ei Chemical Co., Ltd.

[0084] As the 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 phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred as the active ester curing agent. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of 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 phenol compounds 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-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two phenol molecules with one dicyclopentadiene molecule.

[0085] 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 phenol novolac, and active ester curing agents containing a benzoylated phenol novolac. Among these, active ester curing agents containing a naphthalene structure and active ester curing agents containing a dicyclopentadiene-type diphenol structure are more preferred. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0086] Commercially available active ester curing agents include, as active ester curing agents containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "EXB-8000L-65TM" (manufactured by DIC); as active ester curing agents containing a naphthalene structure, "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", and "EXB-8150L-65T" (manufactured by DIC); and phenol novolac Examples of active ester curing agents containing acetylated compounds include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester curing agents containing benzoylated phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); active ester curing agents that are acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester curing agents that are benzoylated phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0087] Examples of amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among these, aromatic amines are preferred. The amine-based curing agent is preferably a primary amine or a secondary amine, with primary amines being more preferred. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, 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-hydroxy Examples include bis(4-(4-aminophenoxy)phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Commercial amine-based curing agents may also be used, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" from Nippon Kayaku Co., Ltd., and "Epicure W" from Mitsubishi Chemical Corporation.

[0088] Examples of acid anhydride-based curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic acid di Examples of acid anhydrides include anhydrides, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. A commercially available acid anhydride-based curing agent is, for example, "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

[0089] Specific examples of benzoxazine-based curing agents 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 Corporation; "Pd" (benzoxazine ring equivalent 217 g / eq.) and "Fa" (benzoxazine ring equivalent 217 g / eq.) manufactured by Shikoku Chemicals Corporation; and "HFB2006M" (benzoxazine ring equivalent 432 g / eq.) manufactured by Showa Polymer Co., Ltd.

[0090] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) thioether, and bis(4-cyanatephenyl) ether; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, etc.; and prepolymers in which these cyanate resins are partially triazined. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazined and trimerized), all manufactured by Lonza Japan.

[0091] Specific examples of carbodiimide-based curing agents include Carbodilite® V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.), V-09 (carbodiimide group equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Corporation, and Stavaxol® P (carbodiimide group equivalent: 302 g / eq.) manufactured by Rhein Chemie.

[0092] Specific examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl) isocyanurate.

[0093] (D) The active group equivalent of the curing agent 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 the curing agent per equivalent of one active group.

[0094] (A) When the number of epoxy groups in the epoxy resin is set to 1, the number of active groups in the curing agent (D) 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. "(A) Number of epoxy groups in epoxy resin" refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the epoxy resin (A) present in the resin composition by the epoxy equivalent. Also, "(D) Number of active groups in curing agent" refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the curing agent (D) present in the resin composition by the active group equivalent.

[0095] 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, based on 100% by mass of the nonvolatile components of the resin composition.

[0096] The amount of 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, based on 100% by mass of the resin component of the resin composition.

[0097] [6. (E) Curing accelerator] The resin composition according to this embodiment may further contain, as an optional component, (E) a curing accelerator in combination with the components (A) to (D) described above. This curing accelerator (E) does not include any of the components (A) to (D) described above. The curing accelerator (E) functions as a curing catalyst that accelerates the curing of the epoxy resin (A).

[0098] (E) Examples of 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. (E) A single type of curing accelerator may be used, or two or more types may be used in combination.

[0099] Examples of phosphorus-based curing accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromelitate, tetrabutylphosphonium hydrogen 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, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium bromide. Aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition products such as triphenylphosphine-p-benzoquinone addition products; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine Examples include aromatic phosphines such as 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.

[0100] Examples of urea-based curing accelerators include aliphatic dimethylureas such as 1,1-dimethylurea, 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)-1,1-dimethylurea. Aromatic dimethylureas such as toluenebisdimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] are examples.

[0101] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0102] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct Examples of imidazole compounds include 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins. Examples of commercially available imidazole-based curing accelerators include "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" from Shikoku Chemicals, Inc., and "P200-H50" from Mitsubishi Chemical Corporation.

[0103] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0104] Examples of amine-based 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 amine-based curing accelerators may also be used, such as "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd.

[0105] 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, based on 100% by mass of the nonvolatile components of the resin composition.

[0106] 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, based on 100% by mass of the resin component of the resin composition.

[0107] [7. (F) Any additives] The resin composition according to this embodiment may further contain (F) any additive as an optional nonvolatile component in combination with the components (A) to (E) described above. Examples of optional additives (F) include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; defoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion ferrites such as triazole-based adhesion ferrites, tetrazole-based adhesion ferrites, and triazine-based adhesion ferrites; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; and fluorine Examples of additives include surfactants such as silicone surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. (F) Any additive may be used alone or in combination of two or more types.

[0108] [8. (G) Solvent] The resin composition according to this embodiment may further contain a solvent (G) as an optional volatile component in combination with the non-volatile components such as components (A) to (F) described above. Typically, an organic solvent is used as the solvent (G). 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; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples include ether ester solvents such as tyl; 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); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide 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) The solvent may be used individually or in combination of two or more types.

[0109] (G) The amount of solvent is not particularly limited, but when the total components in the resin composition are considered to be 100% by mass, it may 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, etc., and may also be 0% by mass.

[0110] [9. Method for producing resin compositions] The resin composition according to this embodiment can be manufactured, for example, by mixing the components described above. The components described above may be mixed some or all at the same time, or they may be mixed sequentially. The temperature may be set appropriately during the mixing of each component, and thus heating and / or cooling may be performed temporarily or throughout the process. Furthermore, stirring or shaking may be performed during the mixing of each component.

[0111] [10. Properties of resin compositions and their cured products] According to the resin composition of this embodiment, a cured product capable of suppressing warping can be obtained. Therefore, when a laminate is obtained by forming a layer of cured resin composition (hereinafter sometimes referred to as the "cured product layer") on a substrate such as a silicon wafer, the amount of warping of the laminate can be reduced. For example, when a laminate is manufactured by the method described in the [Warping Evaluation] section of the examples described later and its amount of warping is measured, the amount of warping can be reduced to 1.5 mm or less.

[0112] According to the resin composition of this embodiment, a cured product with excellent adhesion to the conductive layer can be obtained. Therefore, when a cured product layer of the resin composition is formed so as to be in contact with the conductive layer, delamination between the conductive layer and the cured product 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 examples described later, a copper foil adhesion strength of preferably 0.53 kgf / cm or more, preferably 0.57 kgf / cm or more, and particularly preferably 0.60 kgf / cm or more can be obtained.

[0113] According to the resin composition of this embodiment, a cured product with excellent adhesion to silicon can usually be obtained. Therefore, when a cured product layer of the resin composition is formed so as to be in contact with a component made of silicon, delamination between the component and the cured product 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 Examples described later, it is preferably 550 kgf / cm 2 In particular, a load of 570 kgf / cm² is preferred. 2 In particular, 590 kgf / cm² is preferred. 2 The above Si adhesion strength can be obtained.

[0114] According to the resin composition of this embodiment, a cured product with a low modulus of elasticity can usually be obtained. The inventors believe that the fact that the cured product has such a low modulus of elasticity is one of the reasons why the excellent adhesion and warping suppression effects described above are obtained. For example, when the tensile modulus of the cured product of the resin composition is measured by the method described in the [Measurement of Elastic Modulus] section of the Examples described later, a tensile modulus of 16 GPa or less is preferably obtained, more preferably 15 GPa or less, and particularly preferably 14.5 GPa or less. There is no particular limit to the lower limit, but it may be, for example, 5 GPa or more.

[0115] The resin composition according to this embodiment can typically have a low minimum melt viscosity. Therefore, when sealing with the resin composition, the formation of gaps that are 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 [Measurement of Melt Viscosity] section of the examples described later, 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. There is no particular limit to the lower limit, but it can preferably be 500 poise or more, more preferably 1000 poise or more, and particularly preferably 2000 poise or more.

[0116] Since the resin composition has the properties described above, it can be suitably used as a resin composition for sealing layers, and in particular, it can be suitably used as a resin composition for sealing semiconductors (resin composition for semiconductor sealing), preferably as a resin composition for sealing semiconductor chips (resin composition for semiconductor chip sealing). Furthermore, the resin composition may also be used as a resin composition for insulating layers other than for sealing purposes. For example, the above resin composition can be suitably used as a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for insulating layer of semiconductor chip package), and as a resin composition for forming an insulating layer of a circuit board (including printed wiring board) (resin composition for insulating layer of circuit board).

[0117] Examples of semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package), and fan-in type PLP.

[0118] Furthermore, the aforementioned resin composition may also be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

[0119] Furthermore, the aforementioned resin composition can be used in a wide range of applications where resin compositions are used, such as sheet-like laminated materials like resin sheets and prepregs, solder resists, die bonding materials, hole-filling resins, and component-embedding resins.

[0120] [11. Resin Sheet] A resin sheet according to one embodiment of the present invention comprises a support and a resin composition layer formed on the support. Since the resin composition layer is a layer formed by a resin composition, it usually contains the above-mentioned resin composition, and preferably contains only the above-mentioned resin composition.

[0121] From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 550 μm or less, even more preferably 500 μm or less, 400 μm or less, 350 μm or less, 300 μm or less, or 200 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited and may be, for example, 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0122] Examples of support materials include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

[0123] When using a film made of plastic material as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"); polycarbonate (hereinafter sometimes abbreviated as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"); cyclic polyolefins; triacetylcellulose (hereinafter sometimes abbreviated as "TAC"); polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketones; polyimides; and others. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0124] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil. Among these, copper foil is preferred. As for copper foil, foil made of single-metal copper may be used, or foil made of an alloy of copper with another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0125] The support may be subjected to treatments such as matte finish, corona treatment, or antistatic treatment on the surface that bonds with the resin composition layer.

[0126] Furthermore, as the support, a support with a release layer having a release layer on the surface that bonds with the resin composition layer may be used. Examples of release agents used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Examples of commercially available release agents include the alkyd resin-based release agents "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation. Examples of supports with a release layer include "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipeel" manufactured by Unitika Corporation.

[0127] 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. When using a support with a release layer, it is preferable that the overall thickness of the support with the release layer is within the above range.

[0128] Resin sheets can be manufactured, for example, by applying a resin composition onto a support using a coating device such as a die coater. Alternatively, if necessary, a resin varnish may be prepared by dissolving the resin composition in a solvent, and the resin sheet may be manufactured by applying this resin varnish. By using a solvent, the viscosity can be adjusted to improve the coatability. When a resin varnish is used, the resin varnish is usually dried after application to form a resin composition layer.

[0129] As a solvent, for example, those described as solvents that can be contained in the resin composition may be used. The solvent may be used alone, or two or more may be used in any ratio.

[0130] Drying may be carried out by known methods such as heating or blowing hot air. The drying conditions are such that the solvent content in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the solvent, for example, when using a resin varnish containing 30% to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0131] 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 similar to that of 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 can prevent dirt and other debris from adhering to the surface of the resin composition layer and prevent scratches. If the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. The resin sheet can also be stored by rolling it up.

[0132] The resin sheet can be suitably used to encapsulate semiconductor chips (resin sheet for semiconductor chip encapsulation). Applicable semiconductor chip packages include, for example, fan-out type WLP, fan-in type WLP, fan-out type PLP, and fan-in type PLP. The resin sheet can also be used, for example, to encapsulate circuit boards (resin sheet for circuit board encapsulation).

[0133] Furthermore, the resin sheet can be suitably used to form an insulating layer in the manufacturing of semiconductor chip packages (insulating resin sheet for semiconductor chip packages). For example, the resin sheet can be used to form an insulating layer on a circuit board (resin sheet for the insulating layer of a circuit board). Examples of packages using such substrates include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

[0134] Furthermore, the resin sheet may be used as the material for the MUF (Multi-Unit Interface) used after the semiconductor chip is connected to the substrate.

[0135] Furthermore, resin sheets can be used in a wide range of other applications where high insulation reliability is required. For example, resin sheets can be suitably used to form the insulating layer of circuit boards such as printed wiring boards.

[0136] [12. Circuit board] A circuit board according to one embodiment of the present invention includes a cured product of a resin composition. Typically, a circuit board includes a cured product layer formed of a cured product of a resin composition. This cured product layer can usually function as an insulating layer or a sealing layer, and it is preferable that it functions as a sealing layer. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2). (1) A step of forming a resin composition layer on a substrate. (2) A step of curing the resin composition layer to form a cured product layer.

[0137] In step (1), a substrate is prepared. Examples of substrates include glass epoxy substrates, metal substrates (such as stainless steel or cold-rolled steel sheet (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may also have a metal layer, such as copper foil, on its surface as part of the substrate. For example, a substrate having a peelable first metal layer and a second metal layer on both surfaces may be used. When such a substrate is used, a conductor layer, which 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 carriers, and materials for the conductor layer described later, with copper foil being preferred. An example of a substrate having a metal layer is "Micro Thin," an ultra-thin copper foil with carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0138] Furthermore, a conductive layer may be formed on one or both surfaces of the substrate. In the following description, a component including the substrate and the conductive layer formed on the surface of the substrate may be appropriately referred to as a "substrate with wiring layer". Examples of conductive materials included in the conductive layer include materials containing one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductive material, a single metal may be used, or an alloy may be used. Examples of alloys include alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoint of versatility in conductive layer formation, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy alloys as alloys; are preferred. Among these, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel-chromium alloys are more preferred, with single metal copper being particularly preferred.

[0139] The conductor layer may be patterned, for example, to function as a wiring layer. In this case, the line (circuit width) / space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20 / 20 μm or less (i.e., pitch of 40 μm or less), more preferably 10 / 10 μm or less, even more 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 be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

[0140] The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, even more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

[0141] After preparing the substrate, a resin composition layer is formed on the substrate. If a conductive layer is formed on the surface of the substrate, it is preferable to form the resin composition layer in such a way that the conductive layer is embedded in the resin composition layer.

[0142] The resin composition layer is formed, for example, by laminating a resin sheet and a substrate. This lamination can be performed, for example, by heat-pressing the resin sheet onto the substrate from the support side, thereby bonding the resin composition layer to the substrate. Examples of the member used to heat-press the resin sheet onto the substrate (hereinafter sometimes referred to as the "heat-pressing member") include a heated metal plate (such as a SUS end plate) or a metal roll (such as a SUS roll). It is preferable to press the resin sheet with the heat-pressing member via an elastic material such as heat-resistant rubber, rather than pressing the resin sheet directly onto the substrate, so that the resin sheet can adequately follow the surface irregularities of the substrate.

[0143] Lamination of the substrate and the resin sheet may be carried out, for example, by a vacuum lamination method. Lamination conditions may be as follows: The heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, 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, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

[0144] After lamination, the laminated resin sheets may be smoothed by pressing a heat-sealing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for lamination. Lamination and smoothing may be performed continuously using a vacuum laminator.

[0145] After forming a resin composition layer on a substrate, the resin composition layer is heat-cured to form a cured layer. The heat-curing conditions for 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, more preferably in the range of 170°C to 200°C), and the curing time is in the range of 5 minutes to 120 minutes (preferably in the range of 10 minutes to 100 minutes, more preferably in the range of 15 minutes to 90 minutes).

[0146] Before thermal curing the resin composition layer, the resin composition layer may be subjected to a preheating treatment by heating it at a temperature lower than the curing temperature. For example, prior to thermal 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 110°C or lower, more preferably 70°C or higher but 100°C or lower) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

[0147] As described above, 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 include any additional steps. For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing the circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled off before the thermal curing of the resin composition layer, or after the thermal curing of the resin composition layer.

[0148] A method for manufacturing a circuit board may include, for example, a step of polishing the surface of a hardened layer after forming the 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 using a buff, surface grinding using a rotating grinding wheel, and so on.

[0149] A method for manufacturing a circuit board may include, for example, a step (3) of interlayer connection of conductor layers. A method for interlayer connection includes, for example, drilling holes in the cured material layer. Drilling can form holes such as via holes and through holes in the cured material layer. Methods for forming via holes include, for example, laser irradiation, etching, and mechanical drilling. The dimensions and shape of the via holes may be determined appropriately according to the design of the circuit board. Step (3) may also involve interlayer connection by polishing or grinding the cured material layer.

[0150] After the via holes are formed, it is preferable to perform a step to remove the smear inside the via holes. This step is sometimes called a desmear step. For example, when the conductive layer is formed on the hardened layer by a plating step, a wet desmear treatment may be performed on the via holes. Also, when the conductive layer is formed on the hardened layer by a sputtering step, a dry desmear step such as a plasma treatment step may be performed. Furthermore, the hardened layer may be roughened by the desmear step.

[0151] Furthermore, before forming the conductive layer on the cured layer, a roughening treatment may be performed on the cured layer. This roughening treatment typically roughens the surface of the cured layer, including the inside of the via holes. Either a dry or wet roughening treatment may be used. An example of a dry roughening treatment is plasma treatment. An example of a wet roughening treatment is a method in which swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution are performed in that order.

[0152] After forming via holes, a conductive layer may be formed on the cured material layer. By forming a conductive layer at the location where via holes are formed, the newly formed conductive layer and the conductive layer on the substrate surface become electrically connected, and interlayer connection is established. Examples of methods for forming the conductive layer include plating, sputtering, and vapor deposition. For example, a conductive layer having a desired wiring pattern may be formed by plating the surface of the cured material layer using an appropriate method such as a semi-additive method or a fully additive method. Alternatively, for example, if the support in the resin sheet is a metal foil, a conductive layer having a desired wiring pattern may be formed by a subtractive method. The material of the formed conductive layer may be a single metal or an alloy. Furthermore, this conductive layer may have a single-layer structure or a multi-layer structure containing two or more layers of different types of materials.

[0153] Here, an example of an embodiment for forming a conductive layer on a cured material layer will be described in detail. A plating seed layer is formed on the surface of the cured material layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer in accordance with a desired wiring pattern. After forming an electroplated layer on the exposed plating seed layer by electroplating, the mask pattern is removed. Subsequently, the unnecessary plating seed layer can be removed by etching or other processes to form a conductive layer having the desired wiring pattern.

[0154] The method for manufacturing a circuit board may include a step (4) of removing the substrate. By removing the substrate, a circuit board having a cured layer and a conductive layer embedded in the cured layer is obtained. This step (4) can be performed, for example, when a substrate having a peelable metal layer is used.

[0155] [13. Semiconductor Chip Packages] A semiconductor chip package according to one embodiment of the present invention includes a cured resin composition. Examples of this semiconductor chip package include the following:

[0156] The semiconductor chip package according to the first example includes the circuit board described above and a semiconductor chip mounted on the circuit board. This semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit board.

[0157] The bonding conditions between the circuit board and the semiconductor chip can be any conditions that allow for conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, conditions used in flip-chip mounting of semiconductor chips can be adopted. Alternatively, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

[0158] An example of a bonding method is a method of crimping a semiconductor chip onto a circuit board. The crimping conditions are typically a crimping temperature in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and a crimping time in the range of 1 second to 60 seconds (preferably in the range of 5 seconds to 30 seconds).

[0159] Another example of a bonding method is to bond semiconductor chips to a circuit board by reflow soldering. The reflow conditions may be in the range of 120°C to 300°C.

[0160] After bonding the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. It is preferable to use the resin composition according to the above embodiment as this mold underfill material.

[0161] The semiconductor chip package according to the second example includes a semiconductor chip and a cured resin composition that encapsulates the semiconductor chip. In such a semiconductor chip package, the cured resin composition typically functions as a encapsulation layer. Examples of semiconductor chip packages according to the second example include fan-out type WLP and fan-out type PLP.

[0162] Figure 1 is a schematic cross-sectional view showing a fan-out type WLP as an example of a semiconductor chip package according to one embodiment of the present invention. The semiconductor chip package 100 as a fan-out type WLP includes, for example, a semiconductor chip 110; a sealing layer 120 formed to cover the periphery of the semiconductor chip 110; a redistribution formation layer 130 as an insulating layer, provided on the side of the semiconductor chip 110 opposite to the sealing layer 120; a redistribution layer 140 as a conductor layer; a solder resist layer 150; and bumps 160, as shown in Figure 1.

[0163] The manufacturing method for such semiconductor chip packages is (A) A step of laminating a temporary fixing film onto the substrate, (B) A step of temporarily fixing the semiconductor chip onto a temporary fixing film, (C) A process of forming a encapsulation layer on a semiconductor chip, (D) Steps to peel off the substrate and temporary fixing film from the semiconductor chip, (E) A step of forming a redistribution layer on the surface from which the semiconductor chip substrate and temporary fixing film have been peeled off. (F) A step of forming a redistribution layer as a conductor layer on a redistribution formation layer, and (G) A step of forming a solder resist layer on the redistribution layer, This includes the above. Furthermore, the method for manufacturing the semiconductor chip package is (H) A process of dicing multiple semiconductor chip packages into individual semiconductor chip packages. It may include.

[0164] (Process (A)) Step (A) is a step of laminating a temporary fixing film onto the substrate. The lamination conditions between the substrate and the temporary fixing film may be the same as those for lamination between the substrate and the resin sheet in the manufacturing method of a circuit board.

[0165] Examples of substrates 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 which are made by impregnating glass fibers with epoxy resin and then heat-curing them, and substrates made of bismaleimide triazine resin such as BT resin.

[0166] The temporary fixing film can be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Examples of commercially available products include Nitto Denko's "Riva Alpha".

[0167] (Process (B)) Step (B) is a step of temporarily fixing the semiconductor chip onto a temporary fixing film. Temporary fixing of the semiconductor chip can be performed using equipment such as a flip-chip bonder or die bonder. The layout and number of semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor chip packages to be produced, etc. For example, the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and then temporarily fixed.

[0168] (Process (C)) Step (C) is a step of forming a sealing layer on a semiconductor chip. The sealing layer can be formed by a cured product of the resin composition according to the above embodiment. The sealing layer is usually formed by a method that includes the steps of forming a resin composition layer on a semiconductor chip and thermal curing this resin composition layer to form a cured product layer as a sealing layer. The formation of the resin composition layer on a semiconductor chip can be carried out in the same way as the method for forming a resin composition layer on a substrate described in the circuit board manufacturing method, except that a semiconductor chip is used instead of a substrate.

[0169] After forming a resin composition layer on a semiconductor chip, this resin composition layer is thermally cured to obtain a sealing layer that covers the semiconductor chip. This seals the semiconductor chip with the cured resin composition. The thermal curing conditions for the resin composition layer may be the same as those used in the manufacturing method of a circuit board. Furthermore, before thermal curing the resin composition layer, a preheating treatment may be performed on the resin composition layer, which is heated at a temperature lower than the curing temperature. The processing conditions for this preheating treatment may be the same as those used in the manufacturing method of a circuit board.

[0170] (Process (D)) Step (D) is a step of peeling the substrate and temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate peeling method depending on the material of the temporary fixing film. Examples of peeling methods include peeling by heating, foaming, or expanding the temporary fixing film. Another example of a peeling method is peeling by irradiating the temporary fixing film with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film and then peeling it off.

[0171] In the method of peeling off a temporary fixing film by heating, foaming, or expanding it, the heating conditions are typically 100°C to 250°C for 1 to 90 seconds or 5 to 15 minutes. In the method of peeling off a temporary fixing film by reducing its adhesive strength by irradiating it with ultraviolet light, the amount of ultraviolet light irradiated is typically 10 mJ / cm². 2 ~1000 mJ / cm 2 That is the case.

[0172] As described above, when the substrate and temporary fixing film are peeled off from the semiconductor chip, the surface of the sealing layer is exposed. The method for manufacturing the semiconductor chip package may include polishing this exposed surface of the sealing layer. Polishing can improve the smoothness of the surface of the sealing layer. The same polishing method as described in the method for manufacturing the circuit board can be used.

[0173] (Process (E)) Step (E) is a step of forming a redistribution-forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and temporary fixing film have been peeled off. Typically, this redistribution-forming layer is formed on the semiconductor chip and the sealing layer. The redistribution-forming layer can be formed, for example, from a photosensitive resin composition or a thermosetting resin composition. After forming the redistribution-forming layer, via holes are usually formed in the redistribution-forming layer to connect the semiconductor chip and the redistribution-forming layer.

[0174] (Process (F)) Step (F) is the step of forming a redistribution layer as a conductor layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer may be the same as the method of forming a conductor layer on a cured material layer in the manufacturing method of a circuit board. Alternatively, steps (E) and (F) may be repeated to alternately stack the redistribution layer and the redistribution formation layer (build-up).

[0175] (Process (G)) Step (G) is the step of forming a solder resist layer on the redistribution layer. Any insulating material can be used for the solder resist layer. Among these, photosensitive resin compositions and thermosetting resin compositions are preferred from the viewpoint of ease of manufacturing semiconductor chip packages.

[0176] Furthermore, in step (G), bumping may be performed to form bumps as needed. Bumping can be performed by methods such as solder balls or solder plating. The formation of via holes in the bumping process can be done in the same way as in step (E).

[0177] (Process (H)) The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to form individual pieces. The method of dicing the semiconductor chip packages into individual semiconductor chip packages is not particularly limited.

[0178] A third example of a semiconductor chip package is a semiconductor chip package 100 shown as an example in Figure 1, in which the redistribution layer 130 or solder resist layer 150 is formed from a cured product of the resin composition according to the above embodiment.

[0179] [14. Semiconductor Equipment] A semiconductor device according to one embodiment of the present invention comprises the circuit board or semiconductor chip package described above. Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft, etc.). [Examples]

[0180] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples shown below. In the following description, "parts" and "%" refer to "parts by mass" and "mass%" respectively, unless otherwise specified. Unless otherwise specified, the temperature and pressure conditions were room temperature (25°C) and atmospheric pressure (1 atm).

[0181] [Explanation of inorganic fillers] The inorganic fillers used in the following examples and comparative examples are as follows. Inorganic filler 1: Spherical silica particles (average particle size 1 μm, specific surface area 4.5 m²) surface-treated with an aminosilane coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 ( / g). Inorganic filler 2: Spherical alumina particles (average particle size 1.5 μm, specific surface area 1.6 m²) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 2 ( / g).

[0182] [Manufacturing Example 1: Manufacturing of Elastomer 1] In a reaction vessel, 69 g of bifunctional hydroxyl-terminated polybutadiene (number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1800 g / eq., solids content 100% by mass, manufactured by Nippon Soda Co., Ltd. "G-3000"), 40 g of aromatic hydrocarbon mixed solvent (manufactured by Idemitsu Petrochemical Co., Ltd. "Ipsol 150"), and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. Once homogeneous, the temperature was raised to 50°C, and while stirring, 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g / eq) was added, and the reaction was carried out for approximately 3 hours. Next, the reaction mixture was cooled to room temperature, and then 23 g of cresol novolac resin (DIC Corporation "KA-1160", hydroxyl group equivalent = 117 g / eq.) and 60 g of ethyl diglycol acetate (Daicel Corporation) were added. The mixture was heated to 80°C while stirring and the reaction was carried out for approximately 4 hours. FT-IR reading: 2250 cm⁻¹ -1 The disappearance of the NCO peak was confirmed. The reaction endpoint was considered to be reached upon confirmation of the disappearance of the NCO peak. The reactants were cooled to room temperature and filtered through a 100-mesh filter cloth to obtain elastomer 1 (50% by mass of non-volatile content) having a polybutadiene structure and phenolic hydroxyl groups. The number-average molecular weight was 5500.

[0183] [Manufacturing Example 2: Manufacturing of Elastomer 2] In a reaction vessel, 50 g of bifunctional hydroxyl-terminated polybutadiene (number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1800 g / eq., solids content 100% by mass: "G-3000" manufactured by Nippon Soda Co., Ltd.), 23.5 g of aromatic hydrocarbon mixed solvent ("Ipsol 150" manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. Once uniform, the temperature was raised to 50°C, and while stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) was added, and the reaction was carried out for approximately 3 hours. Next, the reaction mixture was cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and 40.4 g of ethyl diglycol acetate (manufactured by Daicel Corporation) were added. The mixture was heated to 130°C while stirring and the reaction was carried out for approximately 4 hours. FT-IR reading: 2250 cm⁻¹ -1 The disappearance of the NCO peak was confirmed. The reaction endpoint was considered to be reached upon confirmation of the NCO peak's disappearance. The reactants were cooled to room temperature and filtered through a 100-mesh filter cloth to obtain elastomer 2 (50% by mass of non-volatile content) having imide, urethane, and polybutadiene structures. The number-average molecular weight was 13700.

[0184] [Manufacturing Example 3: Manufacturing of Elastomer 3] In a reaction vessel, 80 g of polycarbonate diol (number average molecular weight: approximately 1,000, hydroxyl group equivalent: 500 g / eq., non-volatile content: 100%, manufactured by Kuraray Co., Ltd., "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 Corporation, "ethyl diglycol acetate"). The mixture was then heated to 50°C, and while stirring, 27.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08) was added, and the reaction was carried out for approximately 3 hours. After cooling the reaction mixture to room temperature, 14.3 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent: 161.1 g / eq.), 0.12 g of triethylenediamine, and 84.0 g of diethylene glycol monoethyl ether acetate (Daicel Corporation's "Ethyl Diglycol Acetate") were added. The mixture was heated to 130°C with stirring and the reaction was carried out for approximately 4 hours. FT-IR reading: 2250 cm⁻¹ -1 The disappearance of the NCO peak was confirmed. The reaction was considered terminated upon confirmation of the NCO peak's disappearance. 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 content) having imide, urethane, and polycarbonate structures. The number-average molecular weight was 8500.

[0185] [Example 1] Two parts of liquid chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq., chelate modification amount (phosphate modification amount) 1.0 mass%), four parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical "ZX1059", a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq.), and three parts of bixylenol-type epoxy resin (Mitsubishi Chemical "YX4000H", epoxy equivalent 185 g / eq.) were heated and dissolved in 10 parts of MEK while stirring. After cooling to room temperature, 16 parts of elastomer 1 (50% by mass of nonvolatile content), 10 parts of a phenolic curing agent having a triazine skeleton and novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent of approximately 151 g / eq., 2-methoxypropanol solution with 50% solid content), 1 part of an imidazole curing accelerator (Shikoku Chemicals, Inc.'s "1B2PZ", 1-benzyl-2-phenylimidazole, MEK solution with 5% by mass of solid content), 75 parts of inorganic filler 1, and 10 parts of MEK were mixed and uniformly dispersed in a high-speed rotary mixer, and then filtered through a cartridge filter (ROKITECHNO Corporation's "SHP020") to produce a resin varnish.

[0186] [Example 2] The amount of chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was changed to 1.5 parts, and the amount of elastomer 1 (non-volatile content 50% by mass) was changed to 18 parts. Except for the above, the resin varnish was manufactured in the same manner as in Example 1.

[0187] [Example 3] The amount of chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was changed to 0.7 parts, and the amount of elastomer 1 (non-volatile content 50% by mass) was changed to 19 parts. Except for the above, the resin varnish was manufactured in the same manner as in Example 1.

[0188] [Example 4] The amount of chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was changed to 3 parts, and the amount of elastomer 1 (non-volatile content 50% by mass) was changed to 14 parts. Except for the above, the resin varnish was manufactured in the same manner as in Example 1.

[0189] [Example 5] The amount of chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was changed to 4 parts, and the amount of elastomer 1 (non-volatile content 50% by mass) was changed to 12 parts. Except for the above, the resin varnish was manufactured in the same manner as in Example 1.

[0190] [Example 6] The chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was replaced with a liquid chelate-modified epoxy resin (ADEKA "EP-49-10P2", epoxy equivalent 300 g / eq., chelate modification amount (phosphate modification amount) 1.5 mass%). Except for the above, the resin varnish was manufactured in the same manner as in Example 1.

[0191] [Example 7] The chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was replaced with a liquid chelate-type epoxy resin (ADEKA "EP-49-23", epoxy equivalent 175 g / eq.). Except for the above, the resin varnish was manufactured in the same manner as in Example 1.

[0192] [Example 8] A resin varnish was manufactured in the same manner as in Example 1, except that 75 parts of inorganic filler 2 were used instead of 75 parts of inorganic filler 1.

[0193] [Example 9] A resin varnish was manufactured in the same manner as in Example 1, except that 16 parts of elastomer 2 (50% by mass of non-volatile content) were used instead of 16 parts of elastomer 1 (50% by mass of non-volatile content).

[0194] [Example 10] A resin varnish was manufactured in the same manner as in Example 1, except that 16 parts of elastomer 3 (50% by mass of non-volatile content) were used instead of 16 parts of elastomer 1 (50% by mass of non-volatile content).

[0195] [Example 11] A resin varnish was prepared in the same manner as in Example 1, except that 8 parts of a hydroxyl group-containing acrylic polymer (ARUFON UH-2000, manufactured by Toagosei Co., Ltd., with a weight-average molecular weight of 11,000) were used instead of 16 parts of elastomer 1 (50% by mass of non-volatile content).

[0196] [Example 12] A resin varnish was prepared in the same manner as in Example 1, except that 7.5 parts of a phenol novolac resin (DIC Corporation's "TD-2090-60M", hydroxyl group equivalent approximately 105 g / eq., solids content 60% MEK solution) were used instead of 10 parts of a phenol-based curing agent having a triazine skeleton and novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 50% solids content).

[0197] [Example 13] A resin varnish was prepared in the same manner as in Example 1, except that 10 parts of a naphthalene-based phenolic resin (Nippon Steel Chemical & Material Co., Ltd. "SN485", hydroxyl group equivalent 215 g / eq., solids content 60% MEK solution) were used instead of 10 parts of a phenolic curing agent having a triazine skeleton and novolac structure (DIC Corporation "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 50% solids content).

[0198] [Example 14] A resin varnish was prepared in the same manner as in Example 1, except that 10 parts of an active ester compound (DIC Corporation's "HPC-8000-65T", a toluene solution with toluene content of 65% by mass, containing approximately 223 g / eq. of active groups) was used instead of 10 parts of a phenolic curing agent having a triazine skeleton and novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 50% solids content).

[0199] [Comparative Example 1] A resin varnish was prepared in the same manner as in Example 1, except that a chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was not used.

[0200] [Comparative Example 2] Chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was not used. In addition, the amount of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical "ZX1059", a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq.) was changed to 6 parts. Except for the above, the resin varnish was manufactured in the same manner as in Example 1.

[0201] [Comparative Example 3] Chelate epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was not used. In addition, the amount of inorganic filler 1 was changed to 82 parts. Furthermore, the amount of phenolic curing agent having a triazine skeleton and novolac structure (DIC "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 50% solids) was changed to 18 parts. Except for the above changes, the resin varnish was prepared in the same manner as in Example 1.

[0202] [Comparative Example 4] Chelate-type epoxy resin (ADEKA "EP-49-10P", epoxy equivalent 240 g / eq.) was not used. In addition, the amount of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical "ZX1059", a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq.) was changed to 6 parts. Furthermore, 0.3 parts of a triazine functional group-containing silane coupling agent (Shikoku Chemicals "VD-5", 2,4-diamino-6-triethoxysilanetriazine) was added to the resin varnish as an adhesion imparting agent. Except for the above, the resin varnish was manufactured in the same manner as in Example 1.

[0203] [Manufacturing of resin sheets] As a support, a polyethylene terephthalate film (Toray Industries, Ltd., "Lumirror R80", 38 μm thick, softening point 130°C) treated with an alkyd resin-based release agent (Lintec Corporation, "AL-5") was prepared. On this support, the resin varnish produced in the examples and comparative examples was applied using a die coater so that the thickness of the resin composition layer after drying was 50 μm, and the film was dried at 85°C to 100°C for 4 minutes to obtain a resin sheet.

[0204] [Evaluation of copper foil adhesion strength] <Surface treatment for copper-clad laminates> A double-sided copper-clad epoxy resin laminate with a glass cloth substrate having copper foil on its surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic "R-1766") was prepared. Using a micro-etching agent (MEC "CZ8101"), the laminate was etched to a copper etching depth of 2 μm, and both sides were roughened. The copper-clad laminate obtained in this way is sometimes called a "roughened copper-clad laminate".

[0205] <Lamination of resin sheets> The resin sheets produced in the examples and comparative examples were laminated to one side of a roughened copper-clad laminate using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator "CVP700") so that the resin composition layer was bonded to the roughened copper-clad laminate. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing at 100°C and a pressure of 0.74 MPa for 30 seconds.

[0206] <Copper foil surface preparation> A copper foil (electrolytic copper foil "3EC-III" manufactured by Mitsui Mining & Smelting Co., Ltd., 35 μm thick) was immersed in a micro-etching agent ("MEC Etchbond CZ-8100" manufactured by MEC Corporation) to roughen the glossy surface of the copper foil (1 μm etching).

[0207] <Laminating and curing of copper foil> The support of the resin sheet laminated on the roughened copper-clad laminate was peeled off to expose the resin composition layer. The resin composition layer and copper foil were laminated to this resin composition layer so that the roughened glossy surface was bonded to it. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing at 100°C and a pressure of 0.74 MPa for 30 seconds. Next, the resin composition layer was smoothed by hot pressing at atmospheric pressure, 100°C and a pressure of 0.5 MPa for 60 seconds. Furthermore, the resin composition was cured under curing conditions of 100°C for 30 minutes, followed by 190°C for 90 minutes, to obtain a sample having a layered structure of "roughened copper-clad laminate / cured resin composition layer / copper foil".

[0208] <Measurement and evaluation of the peel strength of copper foil> A cut was made in the copper foil, enclosing a section 10 mm wide and 100 mm long. One end of this section was peeled off and grasped with a gripping device (an autocom-type testing machine "AC-50C-SL" manufactured by TSE Corporation). At room temperature, 20 mm was peeled off vertically at a speed of 50 mm / min, and the load (kgf / cm) was measured to determine the peel strength as the adhesion strength of the copper foil.

[0209] [Evaluation of Si adhesion strength] <Lamination and curing of silicon wafers> The resin sheets produced in the examples and comparative examples were laminated onto one side of a 12-inch silicon wafer (thickness 775 μm) using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator "CVP700") so that the resin composition layer and the silicon wafer were bonded together. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, followed by pressing at 100°C and a pressure of 0.74 MPa for 30 seconds. After lamination, the support of the resin sheet was peeled off. The resin composition was cured under curing conditions of 100°C for 30 minutes, followed by 190°C for 90 minutes, to obtain a laminate having a layer structure of "silicon wafer / cured resin composition layer".

[0210] <Preparation of test specimens> The obtained laminate was cut into 1 cm squares and placed on a ceramic backing plate (11.4 cm square, P / N 901450) with an epoxy adhesive, with the cured layer facing up. Further, stud pins (bolt-shaped tools; 2.7 mm in diameter on the adhesive surface; P / N 901106) were fixed to the cured layer with an epoxy adhesive and heated at 150 °C for 1 hour to bond the stud pins to the cured layer.

[0211] <Stud pull test> Using a Stud pull tester (manufactured by ROMULUS, Quad Group Inc.), the stud pins were pulled at a speed of 2 kgf / sec in a direction perpendicular to the main surface of the cured layer, and the load value (kgf / cm 2 ) at the time when the cured layer peeled off was measured as the Si adhesion strength.

[0212] [Warp evaluation] The resin sheets produced in the examples and comparative examples were laminated on the entire one side of a 12-inch silicon wafer (775 μm thick) using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd.'s two-stage build-up laminator "CVP700") so that the resin composition layer and the silicon wafer were joined. The support of the resin sheet was peeled off to expose the resin composition layer, and another resin sheet was laminated on the surface of the resin composition layer in the same manner, and the support was peeled off. By the above lamination, two resin composition layers (total thickness 100 μm) were formed on one side of the 12-inch silicon wafer. The lamination was carried out under the same conditions as in the above [Si adhesion strength evaluation].

[0213] The obtained laminate was heated in an oven at 100 °C for 30 minutes and then at 190 °C for 90 minutes to cure the resin composition layer, and a laminate having a layer structure of "silicon wafer / resin composition cured layer" was obtained. The end of the obtained laminate was pressed against a horizontal table. The distance between the end of the wafer on the side opposite to the pressed end and the table was measured as the warpage amount. And the warpage was evaluated according to the following criteria. Warp evaluation criteria: "○": The warpage amount is 0 mm or more and 1.5 mm (1500 μm) or less. "×": The warpage amount is greater than 1.5 mm.

[0214] [Measurement of elastic modulus] The resin sheets produced 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. In accordance with Japanese Industrial Standards (JIS K7127), a tensile test was performed on the cured products using a Tensilon universal tester (manufactured by A&D Company, Limited), and the elastic modulus (tensile modulus) of the cured products at room temperature was measured.

[0215] [Measurement of melt viscosity] The support was peeled off from the resin sheets produced in the examples and comparative examples to obtain a resin composition layer. This resin composition layer was compressed in a mold to produce measurement pellets (18 mm in diameter, 1.0 g to 1.1 g). Subsequently, the minimum melt viscosity of these measurement pellets was measured using a dynamic viscoelasticity analyzer (Rheosol-G3000, manufactured by UBM). Specifically, for 1 g of measurement pellets, the dynamic viscoelasticity was measured by raising the temperature in the range from a starting temperature of 60°C to 200°C using an 18 mm diameter parallel plate, and the minimum value was determined. The measurement conditions were a heating rate of 5°C / min, a measurement temperature interval of 2.5°C, a frequency of 1 Hz, and a strain of 5 degrees.

[0216] [result] The results of the above-mentioned examples and comparative examples are shown in the table below. In the table below, the meanings of the abbreviations are as follows. (B) Content rate: (B) Content rate of inorganic filler. Activity group ratio: (A) The number of epoxy groups in the epoxy resin is set to 1, and (D) the number of active groups in the curing agent.

[0217] [Table 1]

[0218] [Table 2] [Explanation of Symbols]

[0219] 100 semiconductor chip packages 110 semiconductor chips 120 sealing layer 130 Rewiring formation layer 140 Redistribution layer 150 solder resist layers 160 Bump

Claims

1. (A) epoxy resin, (B) inorganic filler, and (C) elastomer, (A) The epoxy resin includes (A-1) an epoxy resin containing an epoxy group and a structure having chelating ability, (A) The amount of component is 10% by mass or more and 50% by mass or less, relative to 100% by mass of the resin component of the resin composition. (B) The amount of component is 60% by mass or more and 95% by mass or less, relative to 100% by mass of the nonvolatile components of the resin composition. The amount of component (C) is 1% by mass or more and 20% by mass or less, relative to 100% by mass of the nonvolatile components of the resin composition. (C) A resin composition in which the elastomer is selected from the group consisting of resins containing a polybutadiene structure, and resins containing an imide structure, a urethane structure, and a polycarbonate structure in the molecule.

2. The resin composition according to claim 1, wherein the amount of chelation modification of component (A-1) is 0.3% by mass to 10% by mass.

3. The resin composition according to claim 1 or 2, wherein the ratio W(A-1) / W(C) of the mass of component (A-1) to the mass of component (C) is 0.01 to 1.

0.

4. The resin composition according to any one of claims 1 to 3, wherein the amount of component (A-1) is 0.1% by mass or more and 40% by mass or less, based on 100% by mass of the resin component of the resin composition.

5. The resin composition according to any one of claims 1 to 4, wherein component (C) has a number average molecular weight of 1000 or more.

6. (D) The resin composition according to any one of claims 1 to 5, further comprising a curing agent.

7. (E) The resin composition according to any one of claims 1 to 6, further comprising a curing accelerator.

8. A resin composition according to any one of claims 1 to 7, for use as a sealing layer.

9. A resin composition according to any one of claims 1 to 8, having a minimum melt viscosity of 9000 poise or less.

10. A cured product of the resin composition according to any one of claims 1 to 9.

11. A resin sheet comprising a support and a resin composition layer formed on the support containing the resin composition according to any one of claims 1 to 9.

12. A circuit board comprising a cured product of the resin composition according to any one of claims 1 to 9.

13. A semiconductor chip package comprising a cured product of the resin composition according to any one of claims 1 to 9.

14. A semiconductor device comprising a circuit board according to claim 12 or a semiconductor chip package according to claim 13.

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