resin composition

Abstract

To provide a resin composition which contains an epoxy resin and a resin containing a radically-polymerizable unsaturated group and an alkylene oxide structure in combination, and enables production of a cured product excellent in chemical resistance.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a resin containing a radically-polymerizable unsaturated group and an alkylene oxide structure, (C) a curing agent, and (D) two or more kinds of silane coupling agents, wherein the amount of the component (A) is larger than 100 wt.% of the total of the component (B) and the component (C) by 100 mass%.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition, a cured product obtained using the resin composition, a resin sheet, a circuit board, and a semiconductor device.

Background Art

[0002] For circuit boards such as semiconductor chip packages, a cured product layer may be formed of a cured product of a resin composition. These cured product layers can be used as a sealing layer or an insulating layer. In Patent Document 1, a resin composition containing an epoxy resin, a resin containing a combination of a radically polymerizable unsaturated group and an alkylene oxide structure, and a silane coupling agent has been proposed as a resin composition for forming such a cured product layer.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In order to improve the properties of the cured product layer, two or more types of silane coupling agents may be used. However, as a result of the studies by the present inventors, when a resin composition containing an epoxy resin, a resin containing a combination of a radically polymerizable unsaturated group and an alkylene oxide structure, and two or more types of silane coupling agents was used, the chemical resistance of the formed cured product tended to be poor. Specifically, the cured product of the resin composition tended to have low resistance to an alkaline solution.

[0005] The present invention was conceived in view of the above problems, and includes an epoxy resin, a resin containing a radical-polymerizable unsaturated group and an alkylene oxide structure, and two or more types of silane coupling agents, and can obtain a cured product having excellent chemical resistance; a resin sheet containing the resin composition; a cured product of the resin composition; a circuit board containing the cured product and a method for manufacturing the same; and a semiconductor device including the circuit board; and aims to provide these.

Means for Solving the Problems

[0006] The present inventors intensively studied to solve the above problems. As a result, the present inventors found that a resin composition containing (A) an epoxy resin, (B) a resin containing a radical-polymerizable unsaturated group and an alkylene oxide structure, (C) a curing agent, and two or more types of (D) silane coupling agents, in which the amount of component (A) is more than the total of components (B) and (C), can solve the above problems, and completed the present invention. That is, the present invention includes the following

[0007] <1> A resin composition containing (A) an epoxy resin, (B) a resin containing a radical-polymerizable unsaturated group and an alkylene oxide structure, (C) a curing agent, and two or more types of (D) silane coupling agents, where the amount of component (A) is more than 100% by mass with respect to 100% by mass of the total of components (B) and (C). <2> The resin composition according to <1>, where the ratio of the number of active groups of component (C) to the number of epoxy groups of component (A) is 0.35 or less. <3> The resin composition according to <1> or <2>, containing (E) an inorganic filler. <4> The resin composition according to <3>, where the amount of component (E) is 50% by mass or more with respect to 100% by mass of the non-volatile components of the resin composition. <5> The resin composition according to any one of <1> to <4>, where the amount of component (D) is 2% by mass or more with respect to 100% by mass of component (B). <6> The amount of component (D) is 1% by mass or more relative to 100% by mass of component (C). <1> ~ <5> A resin composition according to any one of the items. <7> For forming an insulating layer or sealing layer, <1> ~ <6> A resin composition according to any one of the items. <8> For forming a hardened layer by compression molding, <1> ~ <7> A resin composition according to any one of the items. <9> It comprises a support and a resin composition layer provided on the support, The resin composition layer <1> ~ <8> A resin sheet comprising the resin composition described in any one of the items. <10> <1> ~ <8> A cured product of the resin composition described in any one of the items. <11> <1> ~ <8> A circuit board comprising a cured product of the resin composition described in any one of the items. <12> <11> A semiconductor device including the circuit board described above. <13> <1> ~ <8> (I) A step of forming a resin composition layer containing the resin composition described in any one of the items, (II) A step of curing the resin composition layer and A method for manufacturing a circuit board, including the method described above. <14> Step (I) includes forming a resin composition layer by compression molding, <13> The method for manufacturing a circuit board as described above. [Effects of the Invention]

[0008] According to the present invention, a resin composition can be provided which contains an epoxy resin, a resin containing a combination of a radically polymerizable unsaturated group and an alkylene oxide structure, and two or more silane coupling agents, thereby obtaining a cured product with excellent chemical resistance; a resin sheet containing the resin composition; a cured product of the resin composition; a circuit board containing the cured product and a method for manufacturing the same; and a semiconductor device equipped with the circuit board. [Brief explanation of the drawing]

[0009] [Figure 1] Figure 1 is a schematic cross-sectional view showing a semiconductor chip package as a circuit board according to an example of the present invention. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented with modifications as appropriate without departing from the scope of the claims and their equivalents.

[0011] In this specification, the term “may have substituents” with respect to a compound or group means both cases where the hydrogen atoms of the compound or group are not substituted with substituents, and cases where some or all of the hydrogen atoms of the compound or group are substituted with substituents.

[0012] <Overview of Resin Composition> A resin composition according to one embodiment of the present invention comprises (A) an epoxy resin, (B) a resin containing radical polymerizable unsaturated groups and an alkylene oxide structure, (C) a curing agent, and two or more types of (D) silane coupling agents. In the following description, "(B) a resin containing radical polymerizable unsaturated groups and an alkylene oxide structure" may be referred to as "(B) a polymerizable alkylene oxide resin." In the resin composition according to this embodiment, the amount of (A) epoxy resin is greater than 100% by mass relative to the total of 100% by mass of (B) the polymerizable alkylene oxide resin and (C) the curing agent.

[0013] This resin composition allows for the production of cured products with excellent chemical resistance. Furthermore, this resin composition generally suppresses the formation of flow marks.

[0014] <(A) Epoxy resin> The resin composition according to this embodiment includes an epoxy resin (A) as component (A). The epoxy resin (A) may be a curable resin having epoxy groups. The epoxy resin (A) may be used alone or in combination of two or more types. The resin composition according to this embodiment contains this epoxy resin (A) in an amount within a specific range.

[0015] Specifically, the amount of (A) epoxy resin is typically more than 100% by mass, preferably 105% or more by mass, more preferably 110% or more by mass, preferably 500% or less by mass, more preferably 400% or less by mass, and even more preferably 300% or less by mass, relative to 100% by mass of the total of (B) polymerizable alkylene oxide resin and (C) curing agent. When the amount of (A) epoxy resin is within the above range, a cured product with excellent chemical resistance can be obtained, and the formation of flow marks can usually be suppressed.

[0016] (A) Examples of epoxy resins 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, glycidyl ester 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, and the like.

[0017] (A) From the viewpoint of obtaining a cured product with excellent heat resistance, the epoxy resin preferably contains an epoxy resin containing an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocyclics. Examples of epoxy resins containing aromatic structures 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, glycidyl ester 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, spiro-ring 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.

[0018] Among these, bisphenol A type epoxy resin, naphthalene type epoxy resin, and glycidylamine type epoxy resin are preferred, with naphthalene type epoxy resin and glycidylamine type epoxy resin being more preferred. When these epoxy resins are used, the chemical resistance of the cured resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0019] (A) The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. (A) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the epoxy resin.

[0020] (A) Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). (A) Epoxy resin may contain only liquid epoxy resin, only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin. In particular, from the viewpoint of obtaining a resin composition with excellent fluidity during compression molding, it is preferable that (A) epoxy resin contains liquid epoxy resin.

[0021] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred. Preferred liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure; bisphenol A type epoxy resin, naphthalene type epoxy resin, and glycidylamine type epoxy resin are more preferred.

[0022] Specific examples of liquid epoxy resins include DIC's "HP-4032", "HP-4032-D", "HP-4032-SS" (naphthalene-type epoxy resin); DIC's "EXA-850CRP" (bisphenol A-type epoxy resin); Mitsubishi Chemical's "828US", "828EL", "jER828EL", "825", "Epicote 828EL" (bisphenol A-type epoxy resin); Mitsubishi Chemical's "jER807", "1750" (bisphenol F-type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac-type epoxy resin); Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine-type epoxy resin); ADEKA's "ED-523T" (glycyrrhizol-type epoxy resin); ADEKA's Examples include EP-3950L and EP-3980S (glycidylamine type epoxy resins); ADEKA's EP-4088S (dicyclopentadiene type epoxy resin); Nippon Steel Chemical & Material's ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX's EX-721 (glycidyl ester type epoxy resin); Daicel's Celoxide 2021P (alicyclic epoxy resin with an ester skeleton); Daicel's PB-3600, Nippon Soda's JP-100 and JP-200 (epoxy resins with a butadiene structure); and Nippon Steel Chemical & Material's ZX1658 and ZX1658GS (liquid 1,4-glycidylcyclohexane type epoxy resins).

[0023] The amount of liquid epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, based on 100% by mass of the resin components in the resin composition. Unless otherwise specified, the resin components in the resin composition refer to the non-volatile components in the resin composition, excluding the inorganic filler (E) described later. If the inorganic filler (E) is surface-treated with a surface treatment agent, the surface treatment agent is classified as a resin component. Therefore, the resin components in the resin composition usually refer to the non-volatile components in the resin composition, excluding the inorganic material particles contained in the inorganic filler (E) described later. Also, unless otherwise specified, the non-volatile components in the resin composition refer to the components in the resin composition excluding the solvent. When the amount of liquid epoxy resin is within the above range, the chemical resistance of the cured resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0024] 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. As the solid epoxy resin, 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 are preferred.

[0025] Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); 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 resins); and DIC's "EXA-7311". "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V", "ESN4 100V (naphthalene-type epoxy resin); "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "Y Examples include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd.; "YX7760" (bisphenol AF type epoxy resin) from Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) from Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) from Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) from Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalein type epoxy resin) from Nippon Kayaku Co., Ltd.

[0026] (A) When the epoxy resin contains a combination of liquid epoxy resin and solid epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 7:1 to 1:7.

[0027] (A) The epoxy equivalent range of the 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. Epoxy equivalent represents the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0028] (A) The weight-average molecular weight (Mw) of the epoxy resin is preferably in the range of 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight-average molecular weight can be measured as a polystyrene equivalent by gel permeation chromatography (GPC).

[0029] (A) The amount of epoxy resin is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. (A) When the amount of epoxy resin is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0030] (A) The amount of epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, based on 100% by mass of the resin component in the resin composition. (A) When the amount of epoxy resin is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0031] The total amount of (A) epoxy resin, (B) polymerizable alkylene oxide resin, and (C) curing agent is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on 100% by mass of the resin component in the resin composition. When the total amount of (A) epoxy resin, (B) polymerizable alkylene oxide resin, and (C) curing agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0032] The total amount of (A) epoxy resin, (B) polymerizable alkylene oxide resin, (C) curing agent, and (D) silane coupling agent is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less, based on 100% by mass of the resin component in the resin composition. When the total amount of (A) epoxy resin, (B) polymerizable alkylene oxide resin, (C) curing agent, and (D) silane coupling agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0033] <(B) Polymerizable alkylene oxide resin> The resin composition according to this embodiment includes (B) a polymerizable alkylene oxide resin as component (B). The (B) polymerizable alkylene oxide resin contains radical polymerizable unsaturated groups and an alkylene oxide structure. The (B) polymerizable alkylene oxide resin can cure the resin composition because its radical polymerizable unsaturated groups can form bonds through radical polymerization reactions. A resin composition containing the (B) polymerizable alkylene oxide resin in combination with (A) epoxy resin and (C) curing agent can usually suppress warping of a circuit board equipped with a cured product of the resin composition because the flexible alkylene oxide structure can relieve stress. However, conventionally, cured products of resin compositions containing a combination of components (A) to (C) tend to have poor chemical resistance and tend to be prone to flow mark formation. In contrast, the resin composition according to this embodiment can improve chemical resistance and, moreover, can usually suppress the formation of flow marks.

[0034] (B) The radical polymerizable unsaturated groups contained in the polymerizable alkylene oxide resin are typically groups containing carbon-carbon unsaturated bonds that are capable of radical polymerization, such as groups containing ethylenically active carbon-carbon double bonds. Preferred specific examples of these radical polymerizable unsaturated groups include vinyl groups, allyl groups, 1-butenyl groups, 2-butenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, maleoyl groups, vinylphenyl groups, styryl groups, and cinnamoyl groups. Among these, α,β-unsaturated carbonyl groups are preferred, with acryloyl groups and methacryloyl groups being more preferred. (B) The number of radical polymerizable unsaturated groups contained in the polymerizable alkylene oxide resin may be one or two or more. Furthermore, the type of radical polymerizable unsaturated group contained in the polymerizable alkylene oxide resin may be one or two or more. (B) The polymerizable alkylene oxide resin may have radical polymerizable unsaturated groups at its molecular termini.

[0035] (B) The alkylene oxide structure contained in the polymerizable alkylene oxide resin is represented by the following formula (1).

[0036] [ka]

[0037] (In equation (1), R 1 (where * represents an alkylene group which may have substituents; * represents a bonding site.)

[0038] In equation (1), R 1 R represents an alkylene group which may have substituents. The number of carbon atoms in this alkylene group is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 5 or less, even more preferably 4 or less, and even more preferably 3 or less. 1 The alkylene group may have 2 carbon atoms. Specific examples of alkylene groups include methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, and hexylene.

[0039] R 1 The substituents that the alkylene group may have include, for example, halogen atoms, hydroxyl groups, alkoxy groups having 1 to 5 carbon atoms, aryl groups having 6 to 10 carbon atoms, amino groups (-NH2), cyano groups (-CN), carboxyl groups (-COOH), epoxy groups, and nitro groups (-NO). 2) , formyl group (-CHO), -N(C 1-5 Alkyl(2,-C(O)OC) 1-5 Examples include alkyl groups, etc. Here, "C 1-5"Alkyl group" represents an alkyl group having 1 to 5 carbon atoms. Among them, an epoxy group, a hydroxy group, an amino group, and a carboxy group are preferable. These substituents may be those capable of reacting with (A) an epoxy resin or (C) a curing agent. (B) A polymerizable alkylene oxide resin having such a reactive substituent can form a crosslinked structure by the reaction of the substituent, so that a cured product having a high elastic modulus and excellent handleability can be obtained. In this specification, even a resin having an epoxy group, a resin containing a radically polymerizable unsaturated group and an alkylene oxide structure is classified as (B) a polymerizable alkylene oxide resin. The substituents may be used singly or in combination of two or more. However, R 1 is particularly preferably an alkylene group having no substituent.

[0040] Specific examples of the alkylene oxide structure include an ethylene oxide structure (-C2H4O-), a propylene oxide structure (-C3H6O-), a butylene oxide structure (-C4H8O-), a pentylene oxide structure (-C5H 10 O-), and a hexylene oxide structure (-C6H 12 O-). Among them, an ethylene oxide structure and a propylene oxide structure are preferable, and an ethylene oxide structure is more preferable.

[0041] (B) The number of alkylene oxide structures contained in the polymerizable alkylene oxide resin may be 1 or 2 or more. Among them, (B) the polymerizable alkylene oxide resin preferably contains 2 or more alkylene oxide structures. Further, when (B) the polymerizable alkylene oxide resin contains 2 or more alkylene oxide structures, those alkylene oxide structures may be the same or different. The range of the number of alkylene oxide structures per molecule contained in (B) the polymerizable alkylene oxide resin is usually 1 or more, preferably 2 or more, and may be 4 or more, 9 or more, 10 or more, or 11 or more. The upper limit is preferably 101 or less, more preferably 90 or less, still more preferably 68 or less, and still more preferably 65 or less.

[0042] (B) The polymerizable alkylene oxide resin may contain a polyalkylene oxide structure in which two or more alkylene oxide structures are continuously bonded together, as represented by the following formula (2).

[0043] [ka]

[0044] In equation (2), n represents an integer greater than or equal to 2. The range of n may be the same as the range of the number of alkylene oxide structures per molecule contained in the polymerizable alkylene oxide resin described above (B). 1 These are, independently of each other, R in equation (1). 1 It represents the same thing.

[0045] A specific example of a polyalkylene oxide structure is the polyethylene oxide structure (-(C2H4O) n -), polypropylene oxide structure (-(C3H6O) n -) Polybutylene oxide structure (-(C4H8O) n Examples include the poly(ethylene oxide-co-propylene oxide) structure, the poly(ethylene oxide-ran-propylene oxide) structure, the poly(ethylene oxide-alt-propylene oxide) structure, and the poly(ethylene oxide-block-propylene oxide) structure. Among these, the polyethylene oxide structure, the polypropylene oxide structure, the poly(ethylene oxide-co-propylene oxide) structure, the poly(ethylene oxide-ran-propylene oxide) structure, the poly(ethylene oxide-alt-propylene oxide) structure, and the poly(ethylene oxide-block-propylene oxide) structure are preferred, the polyethylene oxide structure and the polypropylene oxide structure are more preferred, and the polyethylene oxide structure is even more preferred.

[0046] (B) Examples of polymerizable alkylene oxide resins include resins represented by the following formulas (B-1) to (B-3).

[0047] [ka]

[0048] In equation (B-1), R 1 These are, independently of each other, R in equation (1). 1 It represents the same thing as (B-1). 2 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with hydrogen atoms or methyl groups being preferred. In formula (B-1), n1 represents 1 or an integer of 2 or more. The range of n1 may be the same as the range of the number of alkylene oxide structures per molecule contained in the polymerizable alkylene oxide resin (B) described above.

[0049] In equation (B-1), R 3 R represents a monovalent hydrocarbon group. 3 This may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Furthermore, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. In addition, the aliphatic hydrocarbon group may be linear, branched, or cyclic. 3 Examples include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0050] R 3 The number of carbon atoms in the alkyl group is usually 1 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 3 or less. Specific examples of this alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and cyclohexyl group.

[0051] R 3The number of carbon atoms in the alkenyl group is usually 2 or more, preferably 12 or less, more preferably 6 or less, and even more preferably 3 or less. Specific examples of this alkenyl group include vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-butadienyl group, 1,4-butadienyl group, hexa-1,3-dienyl group, hexa-2,5-dienyl group, hexa-1,3,5-trienyl group, and the like.

[0052] R 3 The number of carbon atoms in the alkynyl group is usually 2 or more, preferably 12 or less, more preferably 6 or less, and even more preferably 3 or less. Specific examples of this alkynyl group include ethynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, and 1,3-butadiinyl group.

[0053] R 3 In this context, the aryl group represents a monovalent hydrocarbon group obtained by removing one hydrogen atom from an aromatic hydrocarbon. This aryl group includes not only monovalent hydrocarbon groups obtained by removing one hydrogen atom from monocyclic compounds (such as benzene, a hydrocarbon compound formed from one aromatic ring), but also monovalent hydrocarbon groups obtained by removing one hydrogen atom from condensed ring compounds (such as naphthalene, a hydrocarbon compound in which two or more aromatic rings are condensed), and monovalent hydrocarbon groups obtained by removing one hydrogen atom from ring aggregate compounds (such as biphenyl, a hydrocarbon compound in which two or more aromatic rings are linked by a single bond). The number of carbon atoms in the aryl group is preferably 6 or more, preferably 20 or less, more preferably 14 or less, and even more preferably 12 or less. Specific examples of aryl groups include the phenyl group, naphthyl group, anthracenyl group, and biphenyl group (a group obtained by removing one hydrogen atom from biphenyl).

[0054] Among the above, R3 The alkyl and aryl groups are preferred, and the methyl, phenyl, and biphenyl groups are more preferred.

[0055] [ka]

[0056] In equation (B-2), R 1 These are, independently of each other, R in equation (1). 1 It represents the same thing. In equation (B-2), R 2 These are, independently, R in equation (B-1). 2 This represents the same thing. In formula (B-2), n2 represents an integer of 1 or 2 or more, and an integer of 2 or more is preferred. The range of n2 may be the same as the range of the number of alkylene oxide structures per molecule contained in the polymerizable alkylene oxide resin (B) described above.

[0057] [ka]

[0058] In equation (B-3), R 1 These are, independently of each other, R in equation (1). 1 It represents the same thing. In equation (B-3), R 2 These are, independently, R in equation (B-1). 2 This represents the same thing. In formula (B-3), m1 and m2 each independently represent 0 or 1, with 1 being preferred. In formula (B-3), n3 and n4 each independently represent 1 or an integer of 2 or more, with an integer of 2 or more being preferred. The sum of n3 and n4 may be the same as the range of the number of alkylene oxide structures per molecule contained in the (B) polymerizable alkylene oxide resin described above.

[0059] In equation (B-3), R 4 R represents a divalent hydrocarbon group. 4This may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Furthermore, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. In addition, the aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the divalent hydrocarbon group is usually between 1 and 20. 4 Examples include alkylene groups having typically 1 to 20 carbon atoms, preferably 1 to 10, and more preferably 1 to 6; cycloalkylene groups having 3 to 20 carbon atoms; alkenylene groups having 2 to 10 carbon atoms; arylene groups having 6 to 10 carbon atoms; aralkylene groups having 7 to 10 carbon atoms; and groups combining these; and so on.

[0060] R 4 Specific examples include alkylene groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene; cycloalkylene groups such as cyclohexylene; alkenylene groups such as vinylene and propenylene; arylene groups such as phenylene, torylene, xylylene, and naphthylene; aralkylene groups such as benzylene, phenylethylene, and phenylpropylene; and groups represented by the following formulas (b1) to (b6). In formulas (b1) to (b6), * represents a bonding site.

[0061] [ka]

[0062] (B) Preferred examples of polymerizable alkylene oxide resins include the resins of the following formulas (b-1) to (b-5).

[0063] [ka]

[0064] (In the above formula, n5, n6, and n7 each independently represent an integer of 1 or 2 or more, and may be the same as n1 in formula (B-1). n8 and n9 each independently represent an integer of 1 or 2 or more, and the sum of n8 and n9 may be the same as the range of the number of alkylene oxide structures per molecule contained in the polymerizable alkylene oxide resin (B) described above. 10 and n 11 Each of these independently represents an integer of 1 or 2 or more, and n 10 and n 11 The total range may be the same as the range of the number of alkylene oxide structures per molecule contained in the polymerizable alkylene oxide resin described above (B).

[0065] (B) Commercially available polymerizable alkylene oxide resins may be used. (B) Examples of commercially available polymerizable alkylene oxide resins include monofunctional acrylates "AM-90G", "AM-130G", and "AMP-20GY" manufactured by Shin Nakamura Chemical Industry Co., Ltd.; difunctional acrylates "A-1000", "A-B1206PE", "A-BPE-20", "A-BPE-30", and "A-3000PER" (resins with n8:n9≈6:13 represented by formula (b-4)) and monofunctional methacrylate "M-20G" (formula (b-1 ); a resin with n5=2 represented by formula (b-1), "M-40G" (a resin with n5=4 represented by formula (b-1)), "M-90G", "M-130G" (a resin with n5≒13 represented by formula (b-1)), "M-230G", "PHE-1G" (a resin with n6=1 represented by formula (b-2)), "A-LEN-10" (a resin with n7=1 represented by formula (b-3)); a bifunctional methacrylate "23G", "BPE-900", "BPE-1300N" (represented by formula (b-5) n 10 +n 11Examples include resins of approximately 30%, such as "1206PE"; "Light Ester BC", "Light Ester 041MA", "Light Acrylate EC-A", and "Light Acrylate EHDG-AT" from Kyoeisha Chemical Co., Ltd.; "FA-023M" from Resonaq Corporation; and "Bremmer® PME-4000", "Bremmer® 50POEO-800B", "Bremmer® PLE-200", "Bremmer® PLE-1300", "Bremmer® PSE-1300", "Bremmer® 43PAPE-600B", and "Bremmer® ANP-300" from NOF Corporation.

[0066] (B) Polymerizable alkylene oxide resins may be used individually or in combination of two or more types.

[0067] (B) The range of radical polymerizable group equivalents for polymerizable alkylene oxide resin is preferably 150 g / eq. or more. More specifically, the radical polymerizable group equivalent of monofunctional (B) polymerizable alkylene oxide resin, which has one radical polymerizable group per molecule, is preferably 150 g / eq. or more, more preferably 250 g / eq. or more, and even more preferably 400 g / eq. or more. Also, the radical polymerizable group equivalent of bifunctional (B) polymerizable alkylene oxide resin, which has two radical polymerizable groups per molecule, is preferably 500 g / eq. or more, more preferably 510 g / eq. or more, and even more preferably 600 g / eq. or more. The upper limit of radical polymerizable group equivalents for (B) polymerizable alkylene oxide resin is preferably 4500 g / eq. or less, more preferably 3000 g / eq. or less, even more preferably 2000 g / eq. or less, and even more preferably 1500 g / eq. or less. Radical polymerizable group equivalent refers to the mass of resin per equivalent of radical polymerizable group equivalent.

[0068] (B) The molecular weight range of the polymerizable alkylene oxide resin is preferably 150 or more. More specifically, the molecular weight of a monofunctional (B) polymerizable alkylene oxide resin having one radical polymerizable group per molecule is preferably 150 or more, more preferably 250 or more, and even more preferably 400 or more. Also, the molecular weight of a bifunctional (B) polymerizable alkylene oxide resin having two radical polymerizable groups per molecule is preferably 1000 or more, more preferably 1020 or more, and even more preferably 1200 or more. The upper limit of the molecular weight of the (B) polymerizable alkylene oxide resin is preferably 5000 or less, more preferably 3000 or less, even more preferably 2500 or less, even more preferably 2000 or less, and even more preferably 1500 or less. When the (B) polymerizable alkylene oxide resin is a polymer, it is preferable that its weight-average molecular weight or number-average molecular weight is within the above range. (B) The weight-average molecular weight and number-average molecular weight of polymerizable alkylene oxide resins can be measured in polystyrene equivalent values ​​by gel permeation chromatography (GPC).

[0069] (B) The amount of polymerizable alkylene oxide resin is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 1.4% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. (B) When the amount of polymerizable alkylene oxide resin is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0070] (B) The amount of polymerizable alkylene oxide resin is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 6% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the resin components in the resin composition. (B) When the amount of polymerizable alkylene oxide resin is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0071] <(C) Hardener> The resin composition according to this embodiment includes a curing agent as component (C). The curing agent (C) reacts with the epoxy resin (A) to form a bond and cure the resin composition. The curing agent (C) does not include components (A) to (B) described above. The curing agent (C) may be used alone or in combination of two or more types.

[0072] (C) Examples of curing agents include acid anhydride resins, activated ester resins, phenolic resins, carbodiimide resins, benzoxazine resins, cyanate ester resins, amine resins, and thiol resins. (C) A single curing agent may be used, or two or more may be used in combination.

[0073] (C) The curing agent preferably contains an acid anhydride resin, and may contain only an acid anhydride resin. Conventional resin compositions containing acid anhydride resins tend to have particularly poor chemical resistance and tend to form flow marks particularly easily. In contrast, the resin composition according to this embodiment can improve chemical resistance and suppress flow marks even when the curing agent (C) contains an acid anhydride resin. Therefore, the advantages of the present invention can be particularly effectively utilized when the resin composition contains an acid anhydride resin.

[0074] As acid anhydride resins, resins having one or more, preferably two or more acid anhydride groups in one molecule can be used. Specific examples of acid anhydride resins 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 bensophenone tetracarboxylic acid di Examples 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 obtained by copolymerizing styrene and maleic acid.

[0075] Examples of commercially available acid anhydride resins include "HNA-100," "MH-700," "MTA-15," "DDSA," and "OSA" from Shin Nippon Rika Co., Ltd.; "YH-306" and "YH-307" from Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" from Resona Corporation; and "EF-30," "EF-40," "EF-60," and "EF-80" from Clay Valley Corporation.

[0076] The amount of acid anhydride resin is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 2.0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 6% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. When the amount of acid anhydride resin is within the above range, the chemical resistance of the cured resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0077] The amount of acid anhydride resin is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the resin components in the resin composition. When the amount of acid anhydride resin is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0078] As the active ester resin, a resin having one or more, preferably two or more, active ester groups per molecule can be used. Among these, as the active ester resin, resins having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred.

[0079] The activated ester resin 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. Particularly from the viewpoint of improving heat resistance, activated ester resins obtained from a carboxylic acid compound and a hydroxy compound are preferred, and activated ester resins obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound are 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.

[0080] Specifically, preferred active ester resins include dicyclopentadiene-type active ester resins, naphthalene-type active ester resins containing a naphthalene structure, active ester resins containing an acetylated phenol novolac, and active ester resins containing a benzoylated phenol novolac, with dicyclopentadiene-type active ester resins being more preferred. Among these, active ester resins containing a dicyclopentadiene-type diphenol structure are preferred as dicyclopentadiene-type active ester resins.

[0081] Commercially available active ester resins include, for example, active ester resins containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation); and active ester resins containing a naphthalene structure such as "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", and "EXB-815 Examples include "0-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", and "EXB-8" (manufactured by DIC Corporation); as a phosphorus-containing active ester resin, "EXB9401" (manufactured by DIC Corporation); as an active ester resin that is an acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester resin that is a benzoylated phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and as an active ester resin containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Corporation).

[0082] As phenolic resins, resins having one or more, preferably two or more, hydroxyl groups (phenolic hydroxyl groups) bonded to aromatic rings such as benzene rings and naphthalene rings per molecule can be used. From the viewpoint of heat resistance and water resistance, phenolic resins having a novolac structure are preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic resins may be used, for example, triazine skeleton-containing phenolic resins may be used. To give a specific example, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, triazine skeleton-containing phenol novolac resins may be used.

[0083] Specific examples of phenolic resins include "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-375" from Nippon Steel Chemical & Material Co., Ltd. Examples include "SN-395"; DIC Corporation's "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M", "KA-1160"; and Gun-ei Chemical Co., Ltd.'s "GDP-6115L", "GDP-6115H", "ELPC75", etc.

[0084] As carbodiimide resins, resins having one or more, preferably two or more, carbodiimide structures in one molecule can be used. Specific examples of carbodiimide resins include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); and poly(phenylenecarbodiimide), poly(na Examples of polycarbodiimides include aromatic polycarbodiimides such as phthalenecarbodiimide, poly(tylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. Examples of commercially available carbodiimide resins include "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-05," "Carbodilite V-07," and "Carbodilite V-09" from Nisshinbo Chemical Co., Ltd., and "Stavaxol P," "Stavaxol P400," and "Hycazil 510" from Lanxess Corporation.

[0085] As the benzoxazine resin, a resin having one or more, preferably two or more, benzoxazine rings in one molecule can be used. Specific examples of benzoxazine resins include "JBZ-OP100D" and "ODA-BOZ" from JFE Chemical Corporation; "HFB2006M" from Showa Polymer Co., Ltd.; and "Pd" and "Fa" from Shikoku Chemicals Co., Ltd.

[0086] As the cyanate ester resin, a resin having one or more, preferably two or more cyanate groups in one molecule can be used. Examples of cyanate ester resins include bifunctional cyanate ester 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 ester resins derived from phenol novolacs and cresol novolacs; and prepolymers in which these cyanate ester resins are partially triazined. Specific examples of cyanate ester resins include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza, as well as "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazined and trimerized).

[0087] As the amine resin, a resin having one or more, preferably two or more, amino groups in one molecule can be used. Examples of amine resins include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc., with aromatic amines being preferred. The amine resin is preferably a primary amine or a secondary amine, with primary amines being more preferred. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), 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-hydroxyphenyl)propyl Examples include pan, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Examples of commercially available amine resins include "SEIKACURE-S" from Seika Corporation; "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" from Nippon Kayaku Co., Ltd.; "Epicure W" from Mitsubishi Chemical Corporation; and "DTDA" from Sumitomo Seika Co., Ltd.

[0088] Examples of thiol-based resins include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl) isocyanurate.

[0089] (C) 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 represents the mass of resin per equivalent of active group. Therefore, for example, the active group equivalent of an acid anhydride-based resin represents the acid anhydride group equivalent, and represents the mass of resin per equivalent of acid anhydride group.

[0090] In one example, the range of the weight-average molecular weight (Mw) of the curing agent (C) may be the same as the range of the weight-average molecular weight (Mw) of the epoxy resin (A).

[0091] The ratio (active groups / epoxy groups) of the number of active groups of the (C) curing agent to the number of epoxy groups of the (A) epoxy resin is preferably within a specific range. Specifically, the range of the ratio (active groups / epoxy groups) is preferably 0.50 or less, more preferably 0.40 or less, and even more preferably 0.35 or less. The lower limit is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. The number of epoxy groups of the (A) epoxy resin refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the (A) epoxy resin present in the resin composition by their epoxy equivalents. The number of active groups of the (C) curing agent refers to the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the (C) curing agent present in the resin composition by their active group equivalents. When the ratio (active groups / epoxy groups) is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0092] (C) The amount of curing agent is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 2.0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 6% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. (C) When the amount of curing agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0093] (C) The amount of curing agent is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the resin component in the resin composition. (C) When the amount of curing agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0094] (C) The amount of curing agent is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, preferably 70% 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 total of (A) epoxy resin and (B) polymerizable alkylene oxide resin. (C) When the amount of curing agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0095] <(D) Silane coupling agent> The resin composition according to this embodiment contains a silane coupling agent as component (D). Since the silane coupling agent as component (D) generally contains both organic and inorganic reactive sites, it can increase the adhesion strength between the cured resin composition and the conductive layer in contact with the cured resin. Furthermore, the resin composition according to this embodiment contains two or more types of silane coupling agents (D).

[0096] (D) The silane coupling agent may be used as a surface treatment agent for (E) the inorganic filler, as described later. Therefore, (D) the silane coupling agent may be adsorbed onto the inorganic material particles contained in (E) the inorganic filler. Alternatively, (D) the silane coupling agent may not be adsorbed onto the inorganic material particles but may be included in the resin composition in a free state within the resin component. For example, a portion of (D) the silane coupling agent may be adsorbed onto the inorganic material particles, while another portion may be free within the resin component.

[0097] Examples of silane coupling agents include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamidic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-3-triethoxysilyl]propylamide)-2,5-Dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyl Examples include ropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea, N-(3-trimethoxysilylpropyl)urea, compounds having an aminotriazine ring and an ethoxysilyl group, etc. Among these, epoxysilane-based silane coupling agents containing epoxy groups and aminosilane-based silane coupling agents containing amino groups are preferred.

[0098] (D) When the silane coupling agent includes an epoxysilane-based silane coupling agent, the amount of the epoxysilane-based silane coupling agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the resin components in the resin composition. When the amount of the epoxysilane-based silane coupling agent is within the above range, the chemical resistance of the cured resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0099] (D) When the silane coupling agent includes an aminosilane-based silane coupling agent, the amount of the aminosilane-based silane coupling agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the resin components in the resin composition. When the amount of the aminosilane-based silane coupling agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0100] (D) When the silane coupling agent includes one or more silane coupling agents selected from the group consisting of epoxysilane-based silane coupling agents and aminosilane-based silane coupling agents, the total amount of the epoxysilane-based silane coupling agent and the aminosilane-based silane coupling agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the resin component in the resin composition. When the total amount of the epoxysilane-based silane coupling agent and the aminosilane-based silane coupling agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0101] (D) A commercially available silane coupling agent may be used. (D) Examples of commercially available silane coupling agents include Shin-Etsu Chemical Co., Ltd.'s "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), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), "LS1375" (3-mercaptopropylmethyldimethoxysilane), and "LS3610" (N-(3-tri Examples include: Ethoxysilylpropyl Urea; "Sira Ace S810" (3-mercaptopropyltrimethoxysilane) manufactured by Chisso Corporation; "SIM6475.0" (3-mercaptopropyltriethoxysilane), "SIM6474.0" (3-mercaptopropylmethyldimethoxysilane), "SIM6473.5C" (mercaptomethyltrimethoxysilane), "SIM6473.0" (mercaptomethylmethyldimethoxysilane), "SIU9055.0" (N-(3-triethoxysilylpropyl)urea), "SIU9058.0" (N-(3-trimethoxysilylpropyl)urea) manufactured by Azmax Corporation; and "VD-5" (a compound having an aminotriazine ring and an ethoxysilyl group) manufactured by Shikoku Chemicals, Inc.

[0102] (D) The amount of silane coupling agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. Unless otherwise specified, the amount of (D) silane coupling agent includes both the amount of silane coupling agent adsorbed onto inorganic material particles as a surface treatment agent, and the amount of silane coupling agent that is not adsorbed onto inorganic material particles and is free in the resin components. When the amount of (D) silane coupling agent is within the above range, the chemical resistance of the cured resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0103] (D) The amount of silane coupling agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the resin components in the resin composition. (D) When the amount of silane coupling agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0104] (D) The amount of silane coupling agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less, based on 100% by mass of the epoxy resin (A) in the resin composition. When the amount of (D) silane coupling agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0105] (D) The amount of the silane coupling agent is preferably 2% by mass or more, more preferably 8% by mass or more, even more preferably 14% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, based on 100% by mass of the polymerizable alkylene oxide resin (B) in the resin composition. When the amount of (D) the silane coupling agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0106] (D) The amount of the silane coupling agent is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, based on 100% by mass of the curing agent (C) in the resin composition. When the amount of (D) the silane coupling agent is within the above range, the chemical resistance of the cured product of the resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0107] The amount of (D) silane coupling agent that is freed in the resin component without being adsorbed onto the inorganic material particles is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the resin component in the resin composition. When the amount of freed (D) silane coupling agent is within the above range, the chemical resistance of the cured resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0108] <(E) Inorganic filler> The resin composition according to this embodiment may contain (E) an inorganic filler as an optional component. The (E) inorganic filler, as component (E), is included in the resin composition in granular form and is usually included in the cured product while maintaining that granular state. Generally, the (E) inorganic filler has a lower coefficient of thermal expansion than the resin component, so it can reduce the thermal expansion of the cured product of the resin composition and suppress warping of the circuit board.

[0109] (E) Inorganic fillers typically contain particles of inorganic material. (E) Inorganic materials used to form inorganic fillers are typically inorganic compounds. Examples of inorganic materials 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. Therefore, (E) inorganic fillers preferably contain silica, and may contain only silica. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred as the silica. (E) The inorganic filler may be used alone or in combination of two or more types.

[0110] (E) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" from Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" from Admatex Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" from Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; "Cellspheres" and "MGH-005" from Taiheiyo Cement Corporation; and "Esferique" and "BA-1" from JGC Catalysts & Chemicals Co., Ltd.

[0111] (E) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, and even more preferably 2 μm or less.

[0112] (E) 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 used in which 100 mg of inorganic filler and 10 g of methyl ethyl ketone are weighed into a vial and dispersed using 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, and the volume-based particle size distribution of the inorganic filler can be measured using a flow cell method. The average particle size can then 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.

[0113] (E) The specific surface area of ​​the inorganic filler is preferably 0.1 m². 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 It is 100m or more / g, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2 It is less than or equal to / g. (E) The specific surface area of ​​the inorganic filler can be measured by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0114] (E) The maximum cut diameter of the inorganic filler is preferably 10 μm or less, more preferably 8 μm or less, even more preferably 6 μm or less, preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more. The maximum cut diameter is a reference diameter set when classifying the particles of the inorganic filler (E), and preferably, particles classified to have a particle size of less than or equal to this maximum cut diameter are used as the inorganic filler (E).

[0115] (E) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. The (E) inorganic filler treated with a surface treatment agent may contain particles of the inorganic material and the surface treatment agent adsorbed on the particles. Examples of surface treatment agents include coupling agents such as (D) silane coupling agents and titanate coupling agents; alkoxysilanes; organosilazane compounds; and among these, (D) silane coupling agents are preferred. Examples of silane coupling agents suitable for surface treatment agents include fluorine-containing silane coupling agents, aminosilane-based silane coupling agents, epoxysilane-based silane coupling agents, and mercaptosilane-based silane coupling agents. The surface treatment agent may be used alone or in any combination of two or more types.

[0116] 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.

[0117] 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.

[0118] 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 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition layer, 1.0 mg / m 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2 The following are even more preferable.

[0119] (E) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after cleaning the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) following surface treatment. Specifically, a sufficient amount of MEK is added to the inorganic filler that has been 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 solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0120] (E) The amount of inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 80% by mass or more, based on 100% by mass of nonvolatile components in the resin composition. The upper limit is preferably 90% by mass or less, more preferably 88% by mass or less, and even more preferably 85% by mass or less. If the inorganic filler (E) is surface-treated, the amount of inorganic filler (E) above includes the amount of the surface treatment agent. When the amount of inorganic filler (E) is within the above range, the chemical resistance of the cured resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0121] The amount of inorganic material particles in the (E) inorganic filler, excluding the surface treatment agent, is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, preferably 90% by mass or less, more preferably 88% by mass or less, and even more preferably 85% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. When the amount of inorganic material particles in the (E) inorganic filler is within the above range, the chemical resistance of the cured resin composition can be made particularly good, and the formation of flow marks can usually be effectively suppressed.

[0122] <(F) Radical Generator> The resin composition according to this embodiment may contain (F) a radical generator as an optional component. The (F) radical generator does not include components (A) to (E) described above. A thermal radical generator is usually used as the (F) radical generator. A thermal radical generator can generate radicals by applying thermal energy, and can therefore accelerate the reaction of the (B) polymerizable alkylene oxide resin. The (F) radical generator may be used alone or in combination of two or more types.

[0123] Examples of thermal radical generators include dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, and t-hexyl peroxy-2-ethylhexanoate; diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, benzoyl toluyl peroxide, and toluyl peroxide; peracid esters such as t-butyl peracetate, t-butyl peroxyoctoate, and t-butyl peroxybenzoate; ketone peroxides; peroxycarbonates; peroxyketals such as 1,1-di(t-amyl peroxy)cyclohexane; 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), and 2,2'-azobis(2-methylbutyro Examples include azonitrile compounds such as nitrile and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); azoamide compounds such as 2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}; azoamidine compounds such as 2,2'-azobis(2-amidinopropane) dihydrochloride and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride; azoalkane compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 4,4'-azobis(4-cyanopentanoic acid); azo compounds having an oxime skeleton such as 2,2'-azobis(2-methylpropionamide oxime); and azo compounds such as 2,2'-azobis(isobutyric acid)dimethyl.

[0124] As a thermal radical generator, one with moderate activity is preferred. Specifically, the 10-hour half-life temperature T10 (°C) of the thermal radical generator is preferably in the range of 50°C to 110°C, more preferably in the range of 50°C to 100°C, and even more preferably in the range of 50°C to 95°C. Examples of commercially available moderate-activity thermal radical generators include "Luperox 531M80" from Arkema Fuji, "Perhexyl® O" from NOF Corporation, and "MAIB" from Fujifilm Wako Pure Chemical Industries, Ltd.

[0125] (F) As a radical generator, a thermal radical generator is preferred in which the difference ΔT (°C) between the mold temperature Tc (°C) during compression molding and the 10-hour half-life temperature T10 (°C) of the thermal radical generator is within a specific range. Specifically, the range of the temperature difference ΔT (°C) is preferably 20°C or higher, more preferably 30°C or higher, and preferably 80°C or lower. Therefore, if the mold temperature Tc (°C) used during compression molding is known, it is preferable to use a thermal radical generator whose temperature difference ΔT (°C) satisfies the above range.

[0126] (F) The range of the amount of radical generator is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition.

[0127] (F) The range of the amount of radical generator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the resin component in the resin composition.

[0128] <(G) Curing accelerator> The resin composition according to this embodiment may contain (G) a curing accelerator as an optional component. The (G) curing accelerator can act as a catalyst in the reaction of the (A) epoxy resin, and thus can accelerate the curing of the resin composition. The (G) curing accelerator as component (G) does not include components (A) to (F) described above. Furthermore, one type of (G) curing accelerator may be used alone, or two or more types may be used in combination.

[0129] (G) 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, amine-based curing accelerators, and the like.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] (G) The amount of the curing accelerator is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition.

[0137] (G) The amount of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on 100% by mass of the resin component in the resin composition.

[0138] <(H) Any additives> The resin composition according to this embodiment may further contain (H) any additive as an optional component. The optional additive as component (H) does not include components (A) to (G) described above. Examples of optional additives (H) include thermoplastic resins; organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; resin additives such as thickeners, defoamers, leveling agents and flame retardants; colorants; and so on. The optional additive (H) may be used alone or in combination of two or more types.

[0139] Examples of colorants include phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, carbon black, and naphthalene black. The amount of colorant is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition.

[0140] <(I) Solvent> The resin composition according to this embodiment may further contain a solvent (I) as an optional volatile component in combination with the non-volatile components such as components (A) to (H) described above. Typically, an organic solvent is used as the solvent (I). 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. (I) A single solvent may be used alone, or two or more may be used in combination.

[0141] (I) The amount of solvent is preferably small. The range of the amount of solvent (I) in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less, based on 100% by mass of the total amount of the resin composition. The lower limit may be 0% by mass or 0.0001% by mass or more.

[0142] <Method for producing resin compositions> The resin composition according to this embodiment can be manufactured, for example, by mixing components that may be included in the resin composition. Therefore, the resin composition can be manufactured by a manufacturing method that includes a step of mixing components (A) to (D). This manufacturing method may also include a step of mixing any components such as components (E) to (I). Components (A) to (I) may be mixed partially or entirely at the same time, or they may be mixed sequentially.

[0143] When manufacturing a resin composition containing an inorganic filler (E) surface-treated with a surface treatment agent, it is preferable that the resin composition be manufactured by a manufacturing method comprising the steps of: mixing the surface treatment agent with the inorganic filler (usually particles of inorganic material) before surface treatment to obtain the surface-treated inorganic filler (E); and mixing the surface-treated inorganic filler (E) with other components. Generally, the surface treatment agent is adsorbed onto the inorganic material particles of the inorganic filler (E), so not all or most of it is released into the resin components.

[0144] Furthermore, when producing a resin composition containing a silane coupling agent (D) that is free in the resin component without being adsorbed onto the inorganic material particles, the method for producing the resin composition may include a step of mixing the silane coupling agent (D) simultaneously with or after mixing the inorganic filler (E) and components other than the inorganic filler (E). Since some or all of the silane coupling agent (D) mixed in this way is not adsorbed onto the inorganic material particles, a resin composition containing a free silane coupling agent (D) in the resin component can be produced.

[0145] In the method for producing the resin composition, the temperature may be set appropriately during the mixing of each component, and thus heating and / or cooling may be performed temporarily or continuously. Furthermore, stirring or shaking may be performed during the mixing of each component.

[0146] <Physical properties of resin compositions and their cured products> There are no restrictions on the state of the resin composition according to this embodiment. The resin composition may be, for example, liquid or solid. Specifically, the resin composition may be a liquid paste. Hereinafter, a liquid resin composition may be referred to as "resin paste". Resin paste can usually have a low viscosity. In one example, the viscosity range of the resin paste at 25°C may be 20 Pa·s to 1000 Pa·s. From the viewpoint of suppressing void generation, it is preferable that the heat loss of the resin paste is 5% or less.

[0147] Furthermore, the resin composition may be in solid form. Generally, solid resin compositions form molded articles having shapes appropriate to their intended use. Examples of such molded articles include sheets, powders, granules, and pellets. These molded articles typically contain only the resin composition. These molded articles can be manufactured, for example, by a suitable molding method such as compression molding.

[0148] By curing the resin composition according to this embodiment, a cured product of the resin composition can be obtained. This cured product can then be used to form the sealing layer and insulating layer of a circuit board. Normally, heat is applied when curing a resin composition, so among the components contained in the resin composition, volatile components such as (I) solvents may volatilize due to the heat during curing. Therefore, the cured product obtained by curing the resin composition may contain non-volatile components such as components (A) to (H) or their reaction products.

[0149] According to the resin composition of this embodiment, a cured product with excellent chemical resistance can be obtained. Specifically, the cured product of the resin composition of this embodiment can have high resistance to alkaline solutions. For example, a chemical resistance evaluation test is performed in which the cured product is immersed in a strong alkaline solution at 70°C for 1 hour, then washed with distilled water and dried at 130°C for 1 hour. In this case, the amount of thickness reduction of the cured product can be reduced. In one example, the amount of reduction is preferably 50 μm or less, more preferably 30 μm or less. If the sample is a resin composition before curing, the resin composition may be molded onto a silicon wafer by compression molding at a temperature of 130°C, a pressure of 6 MPa, and a curing time of 10 minutes, and then heat-cured at 150°C for 60 minutes to obtain a cured product sample, and the above chemical resistance evaluation test may be performed. A specific method for evaluating chemical resistance can be adopted from the method described in <Test 1. Chemical Resistance Evaluation Test> of the Examples described later.

[0150] The resin composition according to this embodiment can generally suppress the formation of flow marks. Therefore, when the resin composition is molded by compression molding, the formation of flow marks on the molded resin composition and its cured product can be suppressed. "Flow marks" refer to flow traces formed by the flow of the resin composition during molding. For example, the resin composition is molded onto a silicon wafer by compression molding at a temperature of 130°C, a pressure of 6 MPa, and a curing time of 10 minutes, and then heat-cured to form a cured product. In this case, the area of ​​flow marks formed on the surface of the cured product can be reduced, and preferably the area occupied by flow marks can be reduced to less than 20% of the total area of ​​the cured product. A specific method for evaluating flow marks can be adopted from the method described in <Test 2. Flow Mark Evaluation Test> of the Examples described later.

[0151] The cured product of the resin composition according to this embodiment can usually have excellent dielectric properties, specifically a low dielectric loss tangent Df. In one example, the dielectric loss tangent Df of the cured product is preferably 0.020 or less, more preferably 0.010 or less, and even more preferably 0.005 or less. There is no particular lower limit, and it can be, for example, 0.0001 or more. The dielectric loss tangent can be measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. If the sample is a resin composition before curing, the resin composition may be heat-cured at 150°C for 60 minutes to obtain a cured product, and the dielectric loss tangent of the cured product may be measured.

[0152] <Uses of resin compositions> The resin composition according to this embodiment can be used, for example, as an insulating layer-forming resin composition for forming an insulating layer, or as an sealing layer-forming resin composition for forming a sealing layer. Since the insulating layer and sealing layer are cured layers formed by cured products of the resin composition, they contain cured products, and usually contain only cured products. These insulating layers and sealing layers are preferably applied to circuit boards such as printed wiring boards and semiconductor chip packages, from the viewpoint of utilizing the excellent dielectric properties of the cured products.

[0153] The resin composition according to this embodiment can have excellent chemical resistance. Therefore, it is preferable to use the resin composition in applications where its chemical resistance can be utilized. For example, a conductive layer may be formed on the sealing layer and insulating layer of a circuit board, and chemicals such as alkaline solutions may be used in the process of forming the conductive layer. Therefore, it is preferable to use the resin composition according to this embodiment to form a sealing layer or a conductive layer on which a conductive layer is formed, as described above. To give specific examples, the resin composition of this embodiment may be used to form the sealing layer and redistribution layer of a semiconductor chip package, and the interlayer insulating layer of a printed wiring board. Unless otherwise specified, "redistribution layer" refers to the insulating layer on which a redistribution layer as a conductive layer is formed.

[0154] Furthermore, since the resin composition according to this embodiment can suppress the formation of flow marks, it is preferable to use it as a resin composition for molding, and more preferably as a resin composition for compression molding. Even when used for these molding applications, the resin composition according to this embodiment can suppress the formation of flow marks and produce a cured product with a good appearance. To give a specific example, the resin composition according to this embodiment may be used as a resin composition for forming a cured product layer by a compression molding method. The cured product layer thus formed can function as the insulating layer or sealing layer described above.

[0155] The resin composition according to this embodiment may be used for applications other than those described above. Examples of such applications include resin sheets, solder resists, underfill materials, die bonding materials, hole-filling resins, component-embedding resins, and the like.

[0156] <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. The resin composition layer contains the above-mentioned resin composition, and preferably contains only the above-mentioned resin composition.

[0157] From the viewpoint of thinning, the thickness of the resin composition layer of the resin sheet is preferably 600 μm or less, more preferably 500 μm or less, even more preferably 400 μm or less, even more preferably 300 μm or less, even more preferably 200 μm or less, and even more preferably 100 μm or less. The lower limit of the thickness of the resin composition layer may be, for example, 1 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 50 μm or more, etc.

[0158] Examples of support materials include plastic film, metal foil, and release paper, with plastic film and metal foil being preferred.

[0159] When using a plastic film 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"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0160] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being 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.

[0161] The support may have surface treatments such as matte finish, corona treatment, or antistatic treatment applied to the surface that bonds with the resin composition layer.

[0162] As the support, a support with a release layer may be used, which has a release layer on the surface that is bonded to the resin composition layer. 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-based release agents, polyolefin-based release agents, urethane-based release agents, and silicone-based release agents. Commercially available products may be used as the support with a release layer, for example, PET films having a release layer mainly composed of a silicone-based release agent or an alkyd resin-based release agent, such as "PET501010", "SK-1", "AL-5", and "AL-7" from Lintec Corporation; "Lumirror T60" from Toray Industries, Inc.; "Purex" from Teijin Ltd.; and "Unipeel" from Unitika Corporation.

[0163] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, preferably 75 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. 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.

[0164] The resin sheet may include any components as needed. For example, the resin sheet may include a protective film to protect the resin composition layer. The protective film is usually 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 not particularly limited, but is, for example, 1 μm to 40 μm. When a protective film is provided, the adhesion of dust and scratches to the surface of the resin composition layer can be suppressed.

[0165] A resin sheet can be manufactured, for example, by a method that includes forming a resin composition layer on a support. Specifically, a resin sheet may be manufactured by using a liquid (varnish-like) resin composition as is, or by preparing a liquid (varnish-like) resin composition by mixing it with a solvent, applying this to a support, and then drying it as necessary to form a thermal resin composition layer. As the solvent, the same solvent as described in (I) above as a component of the resin composition may be used.

[0166] The resin composition can be applied using a coating device such as a die coater. Drying can be carried out by drying methods such as heating or hot air blowing. The drying conditions are not particularly limited, but the solvent content in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although this may vary depending on the boiling point of the solvent, for example, when using a resin composition containing 30% to 60% by mass of solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0167] The manufactured resin sheets can be stored by rolling them up. If the resin sheets have a protective film, they can usually be used after removing the protective film.

[0168] The resin sheet can be used for the same purposes as the resin composition described above. Therefore, the resin sheet can be used, for example, as a resin sheet for forming an insulating layer or a sealing layer, and it is preferable to use it as a resin sheet for forming an insulating layer or a sealing layer of a circuit board. From the viewpoint of taking advantage of the excellent chemical resistance of the resin composition, the aforementioned insulating layer or sealing layer may be used to form the sealing layer and redistribution layer of a semiconductor chip package, as well as the interlayer insulating layer of a printed wiring board. Furthermore, from the viewpoint of taking advantage of the ability to suppress the formation of flow marks, it is preferable to use the resin sheet in molding methods such as compression molding.

[0169] <Circuit board> A circuit board according to one embodiment of the present invention includes a cured product of the resin composition described above. Typically, the circuit board has a cured product layer, and this cured product layer includes a cured product of the resin composition. The cured product layer may contain only a cured product of the resin composition. The cured product layer can function as either an insulating layer or a sealing layer, or both. The thickness of the cured product layer is not particularly limited and can be, for example, in the same range as the thickness of the resin composition layer of a resin sheet. Furthermore, the cured product layer can typically have properties similar to those of the cured product of the resin composition described above.

[0170] A circuit board is, for example, Step (I) of forming a resin composition layer, (II) A step of curing the resin composition layer and It can be manufactured by a manufacturing method that includes [the following].

[0171] In step (I), a resin composition layer is typically formed on a suitable substrate. The formed resin composition layer contains the above-mentioned resin composition, preferably containing only the resin composition. As the substrate, for example, an inner layer substrate may be used. An "inner layer substrate" is a component that serves as the substrate for a circuit board, and examples include glass epoxy substrates, metal substrates (stainless steel, cold-rolled steel sheet (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. The inner layer substrate may also have a conductive layer on one or both sides. The conductive layer on the inner layer substrate may be patterned. An inner layer substrate in which a conductive layer (circuit) is formed on one or both sides of the substrate is sometimes called an "inner layer circuit substrate." Furthermore, an intermediate product on which an insulating layer and / or a conductive layer is to be formed when manufacturing a circuit board is also included in the term "inner layer substrate." In addition, an inner layer substrate equipped with components such as semiconductor chips may be used.

[0172] Furthermore, a removable temporary substrate may be used as the base material. Specifically, a component may be temporarily fixed onto the removable temporary substrate, and a resin composition layer may be formed to embed the component. In this case, after curing the resin composition layer in step (II) described later to form a cured layer, the temporary substrate can be removed to obtain a cured layer with the component embedded inside. Such a removable temporary substrate can be manufactured, for example, by laminating a substrate and a temporary fixing film. 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 in which glass fibers are impregnated with epoxy resin and heat-cured, and substrates made of bismaleimide triazine resin such as BT resin. The temporary fixing film can be a film that can be peeled off from the component and can temporarily fix the component, for example, Nitto Denko's "Riva Alpha".

[0173] The resin composition layer may be formed, for example, by a coating method which includes applying the resin composition onto a substrate and drying it as necessary. Alternatively, the resin composition layer may be formed, for example, by a lamination method which involves stacking a substrate and a resin sheet so that the substrate and the resin composition layer are joined together. From the viewpoint of taking advantage of the ability to suppress the formation of flow marks, it is preferable to form the resin composition layer by a compression molding method.

[0174] Compression molding typically involves placing a resin composition in a mold and applying pressure and, if necessary, heat to the resin composition within the mold to form a resin composition layer. When forming a resin composition layer on a substrate, the substrate may also be placed in the mold. The resin composition placed in the mold may be in liquid or solid form. Therefore, the resin composition placed in the mold may be, for example, a resin paste, a resin powder, a resin granule, or a resin pellet. Alternatively, the aforementioned resin sheet may also be placed in the mold.

[0175] The compression molding method may be carried out, for example, as follows: An upper mold and a lower mold are prepared as molds for compression molding. The resin composition is placed on the substrate. The substrate on which the resin composition is placed is attached to the lower mold. Then, the upper and lower molds are clamped together, and heat and pressure are applied to the resin composition to perform compression molding.

[0176] Furthermore, the compression molding method may be carried out as follows, for example: An upper mold and a lower mold are prepared as molds for compression molding. The resin composition is placed on the lower mold. The base material is attached to the upper mold. Then, the upper and lower molds are clamped together so that the resin composition on the lower mold is in contact with the base material attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0177] Furthermore, the compression molding method may involve, for example, discharging the resin composition filled in the cartridge into a mold, and then applying heat and pressure within the mold to perform compression molding.

[0178] The molding conditions vary depending on the composition of the resin composition, but for example, the mold temperature during molding is preferably 80°C or higher, more preferably 100°C or higher, even more preferably 120°C or higher, preferably 200°C or lower, more preferably 170°C or lower, and even more preferably 150°C or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, even more preferably 5 MPa or higher, preferably 50 MPa or lower, more preferably 30 MPa or lower, and even more preferably 20 MPa or lower. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, even more preferably 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, and even more preferably 20 minutes or less.

[0179] The method for manufacturing a circuit board according to this example includes a step (II) in which a resin composition layer is cured after step (I). By curing the resin composition layer in step (II), a cured layer containing a cured resin composition can be formed.

[0180] The resin composition layer is usually cured by thermal curing. The thermal curing conditions for the resin composition layer may vary depending on the type of resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 130°C to 220°C, and even more preferably 140°C to 210°C. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0181] The method for manufacturing a circuit board may include preheating the resin composition layer at a temperature lower than the curing temperature before the resin composition layer is heat-cured. For example, prior to heat-curing the resin composition layer, the resin composition layer may be preheated at a temperature of typically 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C for typically 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes. Preheating is usually performed after step (I).

[0182] The method for manufacturing the circuit board may include any additional steps in combination with the steps (I) to (II) described above.

[0183] The method for manufacturing a circuit board may include, for example, a step (III) after step (II) in which holes such as via holes and through holes are formed in the cured layer. The method for forming the holes can be selected according to factors such as the composition of the resin composition used to form the cured layer. For example, holes may be formed by processing methods such as drilling, laser processing, and plasma processing, with laser processing being preferred. The dimensions and shape of the holes may be appropriately determined according to the design of the circuit board.

[0184] A method for manufacturing a circuit board may include, for example, a step (IV) of roughening the cured material layer. The roughening treatment can roughen the surface of the cured material layer. In addition, the roughening treatment can remove smear (resin residue) from the cured material layer. Therefore, this roughening treatment is sometimes called "desmear treatment". If holes are formed in step (III), smear may be formed inside those holes, so it is preferable to perform the roughening treatment in step (IV) after step (III) to remove the aforementioned smear.

[0185] The procedure and conditions for the roughening treatment are not particularly limited. For example, the roughening treatment may be carried out by applying swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution to the cured layer in this order.

[0186] Examples of swelling solutions used for roughening treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred as the alkaline solution. Examples of commercially available swelling solutions include "Swelling Dip Securigant P" and "Swelling Dip Securigant SBU" manufactured by Atotec Japan. Swelling treatment with a swelling solution can be carried out, for example, by immersing the cured material layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the cured material layer to an appropriate level, it is preferable to immerse the cured material layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0187] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidation treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the hardened layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotec Japan.

[0188] As the neutralizing solution used for roughening treatment, an acidic aqueous solution is preferred, and a commercially available example is "Reduction Solution Securigant P" manufactured by Attec Japan. Neutralization treatment with a neutralizing solution can be carried out by immersing the treated surface, which has been oxidized with an oxidizing agent, in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability, it is preferable to immerse the object that has been oxidized with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0189] The method for manufacturing a circuit board may include step (V) of forming a conductive layer on a cured material layer. If the method for manufacturing a circuit board includes step (III) or (IV), it is preferable that step (V) of forming the conductive layer be performed after steps (III) and (IV).

[0190] The conductive material used in the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains 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. The conductive layer may be a single-metal layer or an alloy layer. Examples of alloy layers include layers formed from 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, single-metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy are preferred from the viewpoint of versatility in conductive layer formation, cost, and ease of patterning, more preferred are single-metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, more preferred are single-metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy are preferred, and single-metal layers of copper are even more preferred.

[0191] The conductive layer may have a single-layer structure, or it may have a multi-layer structure including two or more single-metal layers or alloy layers made of different types of metals or alloys. When the conductive layer has a multi-layer structure, the layer in contact with the hardened layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0192] The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, and more preferably 5 μm to 30 μm.

[0193] The conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the cured material layer using conventionally known techniques such as the semi-additive method or the fully additive method. From the viewpoint of ease of manufacture, the semi-additive method is preferred. An example of forming the conductor layer by the semi-additive method is shown below.

[0194] First, an electroless plating layer (plating seed layer) is formed on the surface of the hardened material layer by electroless plating. Next, a mask pattern is formed on the formed electroless plating layer, exposing a portion of the electroless plating layer corresponding to the desired wiring pattern. After forming an electroplating layer on the exposed electroless plating layer by electroplating, the mask pattern is removed. Subsequently, the unnecessary electroless plating layer can be removed by etching to form a conductor layer having the desired wiring pattern.

[0195] When a conductive layer is formed on a cured material layer, the method for manufacturing the circuit board may include annealing after the formation of the conductive layer. Annealing can improve the adhesion between the cured material layer and the conductive layer. Annealing can be performed, for example, by heating at 150°C to 210°C for 20 to 180 minutes.

[0196] If a resin composition layer is formed using a resin sheet in step (I), the method for manufacturing a circuit board may include removing the support of the resin sheet after the formation of the resin composition layer. The removal of the support may be performed before step (I), between step (I) and step (II), between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V).

[0197] A method for manufacturing a circuit board may include, for example, forming a hardened layer and then polishing the surface of the hardened layer. For example, the surface of the hardened layer may be polished after step (II), and then steps (III) to (V) may be performed. Examples of polishing methods include chemical mechanical polishing using a chemical mechanical polishing apparatus; mechanical polishing methods such as belt polishing, buff polishing, ceramic polishing, grinding using a surface grinding machine, and surface grinding using a grinding wheel rotation.

[0198] In the method for manufacturing a circuit board, each of the above-described steps may be performed only once or repeated two or more times. For example, steps (I) to (V) may be repeatedly performed to manufacture a circuit board having a multilayer structure, such as a multilayer printed wiring board having multiple insulating layers and conductive layers.

[0199] Examples of circuit boards according to this embodiment include printed circuit boards and semiconductor chip packages. Examples of semiconductor chip packages include fan-in type packages and fan-out type packages. Specifically, examples 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. In these semiconductor chip packages, it is preferable to form a sealing layer or a rewiring layer with a cured product layer containing the cured product of the resin composition described above. However, the circuit board is not limited to those exemplified herein.

[0200] For example, a semiconductor chip package may comprise a printed circuit board having a cured layer and a semiconductor chip mounted on the printed circuit board. Alternatively, for example, a semiconductor chip package may comprise a semiconductor chip and a cured layer that seals at least a portion of the semiconductor chip. The cured layer that seals at least a portion of the semiconductor chip can function as a sealing layer. Furthermore, these can be combined to obtain a semiconductor chip package comprising a printed circuit board, a semiconductor chip mounted on the printed circuit board, and a cured layer that seals at least a portion of the semiconductor chip.

[0201] Such a semiconductor chip package can be manufactured by a manufacturing method that includes a step of bonding a semiconductor chip to a printed circuit board. The bonding conditions between the printed circuit board and the semiconductor chip can be any conditions that allow conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the printed circuit board. For example, conditions used in flip-chip mounting of semiconductor chips may be adopted.

[0202] One bonding method is to crimp the semiconductor chip onto a printed circuit board. The crimping conditions are typically a crimping temperature in the range of 120°C to 240°C (preferably 130°C to 200°C, more preferably 140°C to 180°C) and a crimping time in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds). Another bonding method is to place the semiconductor chip on the printed circuit board and bond it by reflow soldering. The reflow soldering conditions may be in the range of 120°C to 300°C. Bonding may also be performed using an insulating adhesive between the semiconductor chip and the printed circuit board.

[0203] Furthermore, the method for manufacturing a semiconductor chip may include filling the gap between the semiconductor chip and the printed circuit board with an underfill material after bonding the semiconductor chip to the printed circuit board. In this case, the resin composition described above may be used as the underfill material.

[0204] The above-described method for manufacturing a semiconductor chip may include a step of forming a sealing layer as a cured material layer that seals at least a portion of the semiconductor chip. The sealing layer is usually formed after the semiconductor chip is bonded to a printed circuit board. The sealing layer can be formed by a method including the above-described steps (I) to (II).

[0205] Figure 1 is a schematic cross-sectional view showing a semiconductor chip package as a circuit board according to an example of the present invention. Another example of a circuit board is a semiconductor chip package 100, as shown in Figure 1, which includes a redistribution forming layer 130 and a redistribution layer 140. This semiconductor chip package 100 includes a semiconductor chip 110; a sealing layer 120 formed to cover the periphery of the semiconductor chip 110; a redistribution forming 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 conductive layer; a solder resist layer 150; and bumps 160. In this example, one or both of the sealing layer 120 and the redistribution forming layer 130 may be formed by a cured layer containing a cured product of the resin composition described above.

[0206] This semiconductor chip package is, for example, (1) A step of obtaining a temporary substrate by laminating a temporary fixing film onto the substrate, (2) A step of temporarily fixing the semiconductor chip onto a temporary fixing film of a temporary substrate, (3) A step of forming a sealing layer on a semiconductor chip, (4) Steps to peel the temporary substrate from the semiconductor chip, (5) A step of forming a redistribution layer on the surface from which the temporary substrate of the semiconductor chip has been peeled off, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer. The product can be manufactured by a method that includes these steps in this order. In this manufacturing method, the formation of the sealing layer in step (3) or the formation of the rewiring layer in step (5) may be carried out by a method that includes the steps (I) to (II) described above.

[0207] In step (1), a temporary fixing film is laminated onto the substrate to obtain a temporary substrate. For example, the substrate and temporary fixing film described above are used.

[0208] In step (2), the semiconductor chip is temporarily fixed onto a temporary fixing film on a temporary substrate. Typically, the semiconductor chip is temporarily fixed onto the temporary fixing film such that the electrode pad surface of the semiconductor chip is in contact with the temporary fixing film. Temporary fixing of the semiconductor chip can be performed using known 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 and the target number of semiconductor chip packages to be produced. For example, the semiconductor chips may be temporarily fixed in a matrix arrangement of multiple rows and multiple columns.

[0209] In step (3), a sealing layer is formed on the semiconductor chip. The sealing layer may be formed by a cured material layer using a method including steps (I) to (II) described above.

[0210] In step (4), the temporary substrate is peeled off from the semiconductor chip. The method for peeling off the detachable substrate can be appropriately selected depending on the material of the temporary fixing film. For example, methods include peeling off the temporary fixing film by heating and foaming (or expanding) it, and peeling off the temporary fixing film by irradiating it with ultraviolet light through the substrate to reduce its adhesive strength. In the method of peeling off the temporary fixing film by heating and foaming (or expanding) it, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of peeling off the temporary fixing film by irradiating it with ultraviolet light to reduce its adhesive strength, the amount of ultraviolet light irradiated is usually 10 mJ / cm². 2 ~1000 mJ / cm 2 That is the case.

[0211] In step (5), a redistribution layer is formed on the surface from which the temporary substrate of the semiconductor chip has been peeled off. The redistribution layer may be formed by a cured layer using a method including steps (I) to (II) described above. After forming the redistribution layer, via holes may be formed in the redistribution layer to interlayer connect the semiconductor chip and the conductor layer described later. Via holes can be formed, for example, by the method described in step (III).

[0212] In step (6), a redistribution layer is formed on the redistribution formation layer as a conductor layer. The redistribution layer can be formed, for example, by the method described in step (V). Alternatively, steps (5) and (6) may be repeated to alternately stack the conductor layer (redistribution layer) and the redistribution formation layer (insulating layer) (build-up).

[0213] A method for manufacturing a semiconductor chip package may further include (7) a step of forming a solder resist layer on a conductor layer (redistribution layer), (8) a step of forming bumps, and (9) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to form individual pieces.

[0214] The manufacturing method described above involves first setting up a semiconductor chip and then forming a redistribution layer on its electrode pad surface (i.e., chip 1st (Chip-1 st This is an example of a (process). In addition to the chip 1st process, semiconductor chip packages are also produced by first providing a redistribution layer, then providing a semiconductor chip on the redistribution layer so that its electrode pad surface can be electrically connected to the redistribution layer, and then sealing it (i.e., redistribution layer 1st (RDL-1 st It may be manufactured by the ) method. The resin composition according to the above embodiment is Chip-1 st Construction method and RDL-1 st It is applicable regardless of the construction method.

[0215] <Semiconductor device> The aforementioned circuit board can be used in the manufacture of semiconductor devices. The semiconductor device comprises the aforementioned circuit board. 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]

[0216] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities are based on mass unless otherwise specified. Furthermore, the operations described below were carried out in an atmospheric environment at normal temperature and pressure (23°C, 1 atm) unless otherwise specified.

[0217] <Explanation of inorganic fillers> Inorganic filler 1: Spherical silica surface-treated with a surface treatment agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane). Average particle size: 0.5 μm, specific surface area: 10 m² 2 / g, maximum cut diameter: 5μm. The amount of surface treatment agent in the total amount of inorganic filler 1 (100% by mass) is 0.7% by mass.

[0218] Inorganic filler 2: Spherical silica surface-treated with a surface treatment agent (KBM573, N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.). Average particle size: 1.2 μm, specific surface area: 4.7 m² 2 / g, maximum cut diameter: 3μm. The amount of surface treatment agent in the total amount of inorganic filler 2 (100% by mass) is 0.6% by mass.

[0219] Inorganic filler 3: Spherical silica surface-treated with a surface treatment agent (KBM573, N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.). Average particle size: 1.5 μm, specific surface area: 3.5 m² 2 / g, maximum cut diameter: 5μm. The amount of surface treatment agent in the total amount of inorganic filler 3 (100% by mass) is 0.5% by mass.

[0220] <Example 1> 3 parts naphthalene-type epoxy resin (DIC Corporation "HP-4032D", 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent approx. 142 g / eq.), 7 parts glycidylamine-type epoxy resin (ADEKA Corporation "EP-3950L", epoxy equivalent 95 g / eq.), 0.15 parts thermal radical generator (Arkema Fuji Corporation "Luperox 531M80", 10-hour half-life temperature T10: 93.0°C, hydrocarbon solution with 80% peroxide content), 80 parts inorganic filler 1, polymerizable alkylene oxide resin (Shin Nakamura Chemical Co., Ltd.) A resin composition was prepared by uniformly dispersing 4 parts of "M-130G" (methoxypolyethylene glycol methacrylate) manufactured by Gaku Kogyo Co., Ltd., 5 parts of an acid anhydride-based curing agent ("HN-2200" (methyltetrahydrophthalic anhydride) manufactured by Resonaq Co., Ltd.), 0.1 parts of a silane coupling agent ("KBM-403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.), 0.5 parts of a curing accelerator ("2MA-OK-PW" (imidazole-based curing accelerator) manufactured by Shikoku Kasei Kogyo Co., Ltd.) and 0.3 parts of carbon black using a mixer.

[0221] <Example 2> The amount of glycidylamine-type epoxy resin (ADEKA "EP-3950L") was changed to 4 parts. In addition, 3 parts of bisphenol A-type epoxy resin (DIC "EXA-850CRP", epoxy equivalent 172.5 g / eq.) were added. Furthermore, 80 parts of inorganic filler 1 were changed to 80 parts of inorganic filler 2. Except for the above changes, the resin composition was prepared in the same manner as in Example 1.

[0222] <Example 3> The amount of polymerizable alkylene oxide resin (M-130G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) was changed to 2 parts. In addition, 80 parts of inorganic filler 2 were changed to 80 parts of inorganic filler 3. Except for the above changes, the resin composition was manufactured in the same manner as in Example 2.

[0223] <Example 4> The amount of acid anhydride-based curing agent (HN-2200, manufactured by Resonaq) was changed to 3 parts. In addition, 80 parts of inorganic filler 2 were changed to 80 parts of inorganic filler 1. Except for the above changes, the resin composition was manufactured in the same manner as in Example 2.

[0224] <Example 5> Three parts of an acid anhydride-based curing agent (HN-2200, manufactured by Resonaq) were replaced with one part of an amine-based curing agent (Kayahard AA, manufactured by Nippon Kayaku Co., Ltd.). In addition, 0.5 parts of a curing accelerator (2MA-OK-PW, manufactured by Shikoku Chemicals, Inc.) were replaced with 0.2 parts of a curing accelerator (2E4MZ, an imidazole-based curing accelerator, manufactured by Shikoku Chemicals, Inc.). Except for the above changes, the resin composition was manufactured in the same manner as in Example 4.

[0225] <Example 6> The amount of naphthalene-type epoxy resin (DIC Corporation's "HP-4032D") was changed to 5 parts. The amount of glycidylamine-type epoxy resin (ADEKA Corporation's "EP-3950L") was also changed to 5 parts. Furthermore, the amount of polymerizable alkylene oxide resin (Shin Nakamura Chemical Industry Co., Ltd.'s "M-130G") was changed to 1.5 parts. In addition, the amount of acid anhydride-based curing agent (Resonac Corporation's "HN-2200") was changed to 3 parts. Except for the above changes, the resin composition was prepared in the same manner as in Example 3.

[0226] <Example 7> The amount of inorganic filler 1 (80 parts) was changed to inorganic filler 2 (80 parts). In addition, the amount of acid anhydride-based curing agent (HN-2200, manufactured by Resonaq) was changed to 5 parts. Except for the above, the resin composition was manufactured in the same manner as in Example 4.

[0227] <Example 8> The resin composition was prepared in the same manner as in Example 7, except that 4 parts of polymerizable alkylene oxide resin (M-130G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) were replaced with 4 parts of polymerizable alkylene oxide resin (BPE-1300N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ethoxylated bisphenol A dimethacrylate).

[0228] <Example 9> The resin composition was prepared in the same manner as in Example 7, except that 4 parts of polymerizable alkylene oxide resin (M-130G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) were replaced with 4 parts of polymerizable alkylene oxide resin (M-40G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methoxytetraethylene glycol methacrylate).

[0229] <Example 10> The resin composition was prepared in the same manner as in Example 7, except that 4 parts of polymerizable alkylene oxide resin (M-130G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) were replaced with 4 parts of polymerizable alkylene oxide resin (M-20G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., methoxydiethylene glycol methacrylate).

[0230] <Example 11> The resin composition was prepared in the same manner as in Example 7, except that 4 parts of polymerizable alkylene oxide resin (M-130G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) were replaced with 4 parts of polymerizable alkylene oxide resin (A-3000PER polyethylene polypropylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0231] <Example 12> The resin composition was prepared in the same manner as in Example 7, except that 4 parts of polymerizable alkylene oxide resin (M-130G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) were replaced with 4 parts of polymerizable alkylene oxide resin (PHG-1G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., phenoxyethylene glycol methacrylate).

[0232] <Example 13> A resin composition was prepared in the same manner as in Example 7, except that 4 parts of polymerizable alkylene oxide resin (M-130G, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) were replaced with 4 parts of polymerizable alkylene oxide resin (A-LEN-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ethoxylated-o-phenylphenol acrylate).

[0233] <Comparative Example 1> The amount of bisphenol A type epoxy resin (DIC Corporation's "EXA-850CRP") was changed to 2 parts. The amount of naphthalene type epoxy resin (DIC Corporation's "HP-4032D") was also changed to 2 parts. Furthermore, the amount of glycidylamine type epoxy resin (ADEKA Corporation's "EP-3950L") was changed to 3 parts. In addition, the amount of acid anhydride-based curing agent (Resonac Corporation's "HN-2200") was changed to 8 parts. Furthermore, the amount of silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-403") was changed to 0.03 parts. Except for the above changes, the resin composition was prepared in the same manner as in Example 7.

[0234] <Comparative Example 2> Bisphenol A type epoxy resin (DIC Corporation's "EXA-850CRP") was not used. In addition, the amount of polymerizable alkylene oxide resin (Shin Nakamura Chemical Industry Co., Ltd.'s "M-130G") was changed to 5 parts. Furthermore, the amount of acid anhydride-based curing agent (Resonac Corporation's "HN-2200") was increased to 7 parts. Except for the above, the resin composition was prepared in the same manner as in Example 4.

[0235] <Test 1. Chemical Resistance Evaluation Test> A resin composition was compressed and molded on a 12-inch disc-shaped silicon wafer (thickness 775 μm) using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). This compression molding formed a 300 μm thick layer of the resin composition on the silicon wafer.

[0236] Subsequently, the resin composition layer was heat-cured by heating at 150°C for 60 minutes to form a cured layer. This resulted in a laminated sample comprising a silicon wafer and a cured layer formed on the silicon wafer (i.e., a silicon wafer with a cured layer). Multiple test pieces were obtained by cutting this laminated sample into a 5 cm square.

[0237] A strong alkaline solution containing 75% dimethyl sulfoxide, 13% glycol derivative, 10% N-methyl-2-pyrrolidone, and 2% tetramethylammonium hydroxide was prepared. A test piece was immersed in the strong alkaline solution at 70 °C for 1 hour. Then, the test piece was taken out from the strong alkaline solution, washed with distilled water, and dried in an oven at 130 °C for 1 hour to obtain a test piece after the chemical immersion test.

[0238] The thickness of the cured layer of the test piece after chemical immersion was measured. Those with a cured layer thickness of 270 μm or more were judged as "excellent", those with a thickness less than 270 μm and 250 μm or more were judged as "good", and those with a thickness less than 250 μm were judged as "poor".

[0239] <Test 2. Flow mark evaluation test> Using a compression molding device (mold temperature: 130 °C, pressure: 6 MPa, cure time: 10 minutes), a resin composition was compression molded on a 12-inch disc-shaped silicon wafer (thickness 775 μm). By this compression molding, a resin composition layer with a thickness of 300 μm was formed on the silicon wafer.

[0240] Then, it was heated at 150 °C for 60 minutes to thermally cure the resin composition layer to obtain a cured layer. This cured layer was observed, and the flow mark was evaluated according to the following criteria. "Good": The area occupied by the flow mark in the entire surface of the cured layer is less than 20%. "Poor": The area occupied by the flow mark in the entire surface of the cured layer is 20% or more.

[0241] <Results> The results of the examples and comparative examples are shown in the following table. In the following table, the meanings of the abbreviations are as follows. "Acid anhydride group / epoxy group": The ratio of the number of active groups (number of acid anhydride groups) of the acid anhydride-based resin to the number of epoxy groups of the (A) epoxy resin "Amine active hydrogen / epoxy group": The ratio of the number of active groups (number of amine active hydrogens) of the amine-based resin to the number of epoxy groups of the (A) epoxy resin "Silane coupling agent / (B) component": (B) Ratio of silane coupling agent (including surface treatment agent) to 100% by mass of polymerizable alkylene oxide resin "Silane coupling agent / (C) component": The ratio of the silane coupling agent (including surface treatment agent) to 100% by mass of the (C) hardener. "A / (B+C)": The ratio of (A) epoxy resin to 100% by mass of the total of (B) polymerizable alkylene oxide resin and (C) curing agent.

[0242] [Table 1]

[0243] [Table 2] [Explanation of Symbols]

[0244] 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 resin composition comprising (A) an epoxy resin, (B) a resin containing a radically polymerizable unsaturated group and an alkylene oxide structure, (C) a curing agent, and two or more types of (D) silane coupling agents, The amount of component (A) is greater than 100% by mass relative to the total of components (B) and (C) (100% by mass), (C) Component contains an acid anhydride resin, A resin composition in which the amount of acid anhydride-based resin is 3% by mass or more and 30% by mass or less, relative to 100% by mass of the resin components of the resin composition.

2. The resin composition according to claim 1, wherein the ratio of the number of active groups of component (C) to the number of epoxy groups of component (A) is 0.35 or less.

3. (E) The resin composition according to claim 1, comprising an inorganic filler.

4. The resin composition according to claim 3, wherein the amount of component (E) is 50% by mass or more relative to 100% by mass of the nonvolatile components of the resin composition.

5. The resin composition according to claim 1, wherein the amount of component (D) is 2% by mass or more relative to 100% by mass of component (B).

6. The resin composition according to claim 1, wherein the amount of component (D) is 1% by mass or more relative to 100% by mass of component (C).

7. A resin composition according to claim 1 for forming an insulating layer or a sealing layer.

8. The resin composition according to claim 1 for forming a cured layer by compression molding.

9. It comprises a support and a resin composition layer provided on the support, A resin sheet in which the resin composition layer comprises the resin composition according to any one of claims 1 to 8.

10. A cured product of the resin composition according to any one of claims 1 to 8.

11. A circuit board comprising a cured product of the resin composition according to any one of claims 1 to 8.

12. A semiconductor device comprising the circuit board described in claim 11.

13. A step (I) of forming a resin composition layer containing the resin composition according to any one of claims 1 to 8, The process of curing the resin composition layer (II) A method for manufacturing a circuit board, including the method described above.

14. The method for manufacturing a circuit board according to claim 13, wherein step (I) includes forming a resin composition layer by compression molding.

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