Curable resin composition, adhesive film, laminate sheet, cured product, and semiconductor device

Abstract

Provided is a curable resin composition that exhibits excellent transferability when formed into an adhesive film. Also provided are an adhesive film and a laminate sheet that exhibit excellent transferability, a cured product of the adhesive film, and a semiconductor device comprising the cured product.　The curable resin composition contains a thermosetting resin (A) and an inorganic filler (C), and further contains a silane coupling agent (D) or contains an inorganic filler (C2) that is modified with the silane coupling agent (D) and serves as the inorganic filler (C). The curable resin composition satisfies formula (1).　Formula (1): G / R ≥ R160 (In the formula, G represents the glossiness (%) of the curable resin composition at an angle of incidence of 60° while in a B-stage state. R represents the maximum height roughness Rz (μm) of the curable resin composition while in the B-stage state.)

Description

Curable resin composition, adhesive film, laminated sheet, cured product, and semiconductor device

[0001] The present invention relates to a curable resin composition, an adhesive film, a laminated sheet, a cured product, and a semiconductor device.

[0002] Along with the higher performance and miniaturization of electronic devices in recent years, mounting technology for semiconductor devices and electronic components has undergone great evolution. In particular, as high-density mounting of semiconductor elements is required, bonding technology for semiconductor elements mounted on circuit boards has been gaining importance. Among these, a technology of applying an adhesive film made of a resin composition between a semiconductor element and a circuit board to bond them has attracted attention. Such an adhesive film is required to have not only the performance to ensure electrical insulation, heat resistance and heat dissipation of electronic components and semiconductor devices, but also the performance to improve mechanical strength.

[0003] The adhesive film is laminated with a base material and used in the form of a laminated sheet. For example, after attaching the adhesive film surface of the laminated sheet to a substrate, the base material is peeled off to form a laminate of the substrate and the adhesive film. Further, another substrate is bonded to the exposed surface of the adhesive film of the laminate, and the adhesive film is cured by heating, thereby bonding the substrates to each other. In addition, by a similar method, it is also possible to bond a substrate and a semiconductor (use as an insulating adhesive layer) or to seal a semiconductor on a substrate (use as a sealing material).

[0004] Regarding such bonding technology, Patent Document 1 discloses an insulating adhesive film for semiconductors containing polyimide resin, epoxy resin, phenol resin, and an inorganic filler as essential components for the purpose of improving the insulation, heat dissipation, and low expansion properties of the adhesive film. A laminated sheet in which this adhesive film for semiconductors is provided on a peeling support base material is also disclosed.

[0005] Japanese Unexamined Patent Publication No. 2004-319823

[0006] However, the adhesive film described in Patent Document 1 had the problem of poor transferability to glossy substrates such as copper foil and wafers. Specifically, when the laminated sheet described in Patent Document 1 was used for lamination to a glossy substrate, delamination occurred at the interface between the substrate and the adhesive film when peeling off the substrate, making it impossible to transfer the adhesive film to the substrate. Poor transferability of the adhesive film is thought to be due to (1) low laminating (adhesion) properties of the adhesive film to glossy substrates, and (2) low peelability of the adhesive film to the substrate. Poor transferability of the adhesive film reduces workability and also negatively affects post-processing in semiconductor device manufacturing. Therefore, adhesive films are required to have excellent transferability.

[0007] Therefore, an object of the present invention is to provide a curable resin composition that exhibits excellent transferability when used as an adhesive film. Another object is to provide an adhesive film and laminated sheet exhibiting excellent transferability, a cured product of the adhesive film, and a semiconductor device comprising the cured product.

[0008] The inventors of this invention conducted extensive research to achieve the above objectives and found that the above problems can be solved when the glossiness and surface roughness in the B-stage state satisfy a certain relationship. This invention was completed based on these findings.

[0009] In other words, the present invention provides a curable resin composition comprising a thermosetting resin (A) and an inorganic filler (C), further comprising a silane coupling agent (D), or an inorganic filler (C2) modified with a silane coupling agent as the inorganic filler (C), wherein the curable resin composition satisfies the following formula (1): G / R ≥ 160 (1) (wherein G represents the gloss (%) at an incident angle of 60° in the B-stage state of the curable resin composition. R represents the maximum height roughness Rz (μm) in the B-stage state of the curable resin composition.)

[0010] Preferably, the above-mentioned curable resin composition further contains at least one selected from the group consisting of a curing agent (B1) and a curing accelerator (B2).

[0011] The above curable resin composition preferably has a gloss level of 80 to 120%.

[0012] The above curable resin composition preferably contains a silane coupling agent having a phenylamino group as the silane coupling agent (D).

[0013] The above curable resin composition preferably contains alumina or a surface-treated alumina as an inorganic filler (C).

[0014] In the above curable resin composition, it is preferable that the content of the silane coupling agent (D) relative to the inorganic filler (C) (100% by mass) is 0.03 to 3% by mass.

[0015] The above curable resin composition preferably has a TI value (1 rpm / 10 rpm) of 0.5 to 1.5 at 25°C.

[0016] The present invention also provides an adhesive film using the above-mentioned curable resin composition.

[0017] The present invention also provides a laminated sheet comprising the above-mentioned adhesive film and a substrate.

[0018] Preferably, the laminated sheet has at least one surface of the substrate that has been subjected to a non-silicone release treatment, and an adhesive film is laminated on the surface.

[0019] In the laminated sheet described above, it is preferable that the base material is a PET film.

[0020] Preferably, the laminated sheet has a contact angle of 70 to 120° with respect to pure water on the surface of the substrate.

[0021] Preferably, the laminated sheet has a 31B tape peel strength of 100 mN / 25 mm or more on the surface of the substrate.

[0022] The above-mentioned laminated sheet is preferably used to laminate a semiconductor substrate.

[0023] The present invention also provides a cured product of the above-mentioned adhesive film.

[0024] The present invention also provides a semiconductor device comprising the above-mentioned cured product and a semiconductor element and / or semiconductor substrate.

[0025] The curable resin composition of the present invention exhibits excellent transferability when used as an adhesive film. Therefore, adhesive films and laminated sheets made from the above curable resin composition exhibit excellent transferability, improving workability. Furthermore, the cured adhesive film and the semiconductor device equipped with the cured film have high reliability.

[0026] [Curable Resin Composition] The curable resin composition of the present invention comprises a thermosetting resin (A) and an inorganic filler (C), and further comprises a silane coupling agent (D), or an inorganic filler (C2) modified with a silane coupling agent as the inorganic filler (C), and satisfies the following formula (1): G / R ≥ 160 (1)

[0027] In formula (1), G represents the gloss (%) at an incident angle of 60° in the B-stage state of the curable resin composition. R represents the maximum height roughness Rz (μm) in the B-stage state of the curable resin composition.

[0028] In other words, one embodiment of the curable resin composition comprises a thermosetting resin (A), an inorganic filler (C), and a silane coupling agent (D), and satisfies formula (1). Another embodiment of the curable resin composition comprises a thermosetting resin (A) and an inorganic filler (C2) modified with a silane coupling agent as the inorganic filler (C), and satisfies formula (1).

[0029] Here, Stage B (state) is synonymous with Stage B among Stages A, B, and C as defined in JIS K6900:1994. Specifically, Stage A refers to the initial stage in the preparation of certain thermosetting resins, in which the material is still soluble and fusible in certain liquids. Stage B refers to the intermediate stage in the reaction of certain thermosetting resins, in which the material swells when it comes into contact with certain liquids and softens when heated, but does not completely dissolve or melt. Stage C refers to the final stage in the reaction of certain thermosetting resins, in which the material becomes virtually insoluble and infusible.

[0030] The gloss (%) (i.e., G in formula (1)) at an incident angle of 60° in the B-stage state of the above curable resin composition is not particularly limited, but is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, and particularly preferably 80% or more. Also, is preferably 140% or less, more preferably 130% or less, even more preferably 120% or less, and particularly preferably 115% or less. Also, is preferably 50 to 140%, more preferably 60 to 130%, even more preferably 70 to 120%, and particularly preferably 80 to 115%. The gloss can be measured by the method described in the examples below.

[0031] The maximum height roughness Rz (μm) (i.e., R in formula (1)) of the above curable resin composition in the B-stage state is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.15 μm or more, even more preferably 0.18 μm or more, even more preferably 0.2 μm or more, and particularly preferably 0.22 μm or more. Also, is preferably 0.8 μm or less, more preferably 0.7 μm or less, even more preferably 0.6 μm or less, even more preferably 0.55 μm or less, even more preferably 0.5 μm or less, even more preferably 0.45 μm or less, and particularly preferably 0.42 μm or less. Also, is preferably 0.1 to 0.8 μm, more preferably 0.15 to 0.7 μm, even more preferably 0.2 to 0.55 μm, and particularly preferably 0.22 to 0.45 μm.

[0032] The arithmetic mean surface roughness Ra (μm) of the above curable resin composition in the B-stage state is not particularly limited, but is preferably 0.005 μm or more, more preferably 0.01 μm or more, even more preferably 0.015 μm or more, even more preferably 0.02 μm or more, and particularly preferably 0.025 μm or more. Also, is preferably 0.2 μm or less, more preferably 0.15 μm or less, even more preferably 0.1 μm or less, even more preferably 0.08 μm or less, even more preferably 0.07 μm or less, and particularly preferably 0.06 μm or less. Also, is preferably 0.005 to 0.2 μm, more preferably 0.01 to 0.15 μm, even more preferably 0.015 to 0.1 μm, and particularly preferably 0.025 to 0.06 μm. Ra and Rz can be measured by the method specified in JIS B 0601:2013 (in accordance with the international standard ISO 4287-1997). More specifically, Ra and Rz can be measured by the method described in the examples below.

[0033] In the curable resin composition described above, the G / R value in formula (1) is not particularly limited as long as it is 160 or more, but for example, it is preferably 170 or more, more preferably 180 or more, even more preferably 190 or more, and particularly preferably 200 or more. Also, for example, it is preferably 800 or less, more preferably 700 or less, even more preferably 600 or less, and particularly preferably 500 or less. Also, for example, it is preferably 160 to 800, more preferably 170 to 700, even more preferably 180 to 600, even more preferably 190 to 600, and particularly preferably 200 to 500.

[0034] The gloss (%) (G in formula (1) above) is a parameter that varies depending on the components contained in the curable resin composition, but can be adjusted mainly by the type and content of the inorganic filler (C) and silane coupling agent (D). Similarly, Rz (μm) (R in formula (1) above) is also a parameter that varies depending on the components contained in the curable resin composition, but can be adjusted mainly by the type of thermosetting resin (A), the type of curing agent (B1) or curing accelerator (B2), and the type and content of the inorganic filler (C) and silane coupling agent (D). Therefore, the G / R value in formula (1) above can be adjusted mainly by appropriately selecting the above components and their contents.

[0035] In particular, the following (a) to (e) are possible means for adjusting the G / R value in formula (1) above to 160 or more. It is not necessary to select all of these means, and by appropriately selecting one or more of them, the G / R value in formula (1) above can be adjusted to 160 or more. (a) By using at least one resin selected from the group consisting of epoxy resin, maleimide resin, polyimide compound, polyphenylene ether resin, siloxane compound, and (meth)acrylate compound as the thermosetting resin (A), the gloss (%) at an incident angle of 60° (i.e., "G") in the B-stage state of the curable resin composition tends to increase. Also, the maximum height roughness Rz (μm) (i.e., "R") in the B-stage state of the curable resin composition tends to decrease. For this reason, the G / R value in formula (1) can be adjusted to 160 or more. Although the reason is not entirely clear, the curable resin composition of the present invention contains an inorganic filler (C) and a silane coupling agent (D), or an inorganic filler (C2) modified with a silane coupling agent. It can be inferred that the dispersibility of the inorganic filler in the resin is improved by the silane coupling agent, and as a result when the material reaches the B stage, surface irregularities caused by the inorganic filler are reduced, resulting in increased gloss and a smaller maximum height roughness Rz. This tendency is more pronounced when epoxy resin is used as the thermosetting resin (A), and it can be inferred that it becomes even more pronounced when the epoxy resin content relative to the thermosetting resin (A) increases. (b) When solid epoxy resin is included as the thermosetting resin (A), the moldability to the B stage (in other words, "film") is improved, and as a result of reduced surface irregularities caused by the inorganic filler, it can be inferred that gloss increases and the maximum height roughness Rz becomes smaller. This tendency is presumed to become more pronounced when the content of solid epoxy resin relative to thermosetting resin (A) increases. As a result, the G / R value in formula (1) can be adjusted to 160 or more. (c) By using an inorganic filler with a relatively small average particle size (for example, 0.01 to 6 μm), there is a tendency for "G" to increase and "R" to decrease. For this reason, the G / R value in formula (1) can be adjusted to 160 or more.Although the reason is not clear, it can be inferred that because the average particle size of the inorganic filler is relatively small, when the material is in the B stage state, surface irregularities caused by the inorganic filler are reduced, resulting in increased gloss and a smaller maximum height roughness Rz. (d) When the above curable resin composition contains at least one selected from the group consisting of amine-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, active ester-based curing agents, and dicyandiamide as the curing agent (B1), the moldability to the B stage is improved, and it can be inferred that surface irregularities caused by the inorganic filler are reduced, resulting in increased gloss and a smaller maximum height roughness Rz. As a result, the value of G / R in formula (1) can be adjusted to 160 or more. (e) When the above curable resin composition contains a silane coupling agent having a phenylamino group as the silane coupling agent (D), the surface of the thermosetting resin (A) and the inorganic filler (C) become more easily chemically bonded. As a result, the inorganic filler (C) is firmly encapsulated within the thermosetting resin (A), making it less likely for the inorganic filler to appear on the surface of the B stage. Consequently, when the curable resin composition is in the B stage state, surface irregularities caused by the inorganic filler are reduced, the glossiness increases, and the maximum height roughness Rz decreases. As a result, the G / R value in formula (1) can be adjusted to 160 or more. Furthermore, if the inorganic filler (C) includes an inorganic filler whose surface is modified with a silane coupling agent having a phenylamino group, the wettability at the interface between the thermosetting resin (A) and the inorganic filler is improved, making it less likely for the inorganic filler to appear on the surface of the B stage. In addition, the inorganic filler becomes less prone to aggregation due to the surface treatment and is uniformly dispersed in the curable resin composition. As a result, it can be inferred that when the above curable resin composition is in the B stage state, surface irregularities caused by the inorganic filler are reduced, glossiness increases, and the maximum height roughness Rz decreases. Consequently, the value of G / R in formula (1) can be adjusted to 160 or more.

[0036] Glossiness and Rz are both indicators of the degree of surface roughness of an object, and are thought to have a certain degree of correlation. However, in the field of this technology, this is not necessarily the case for surfaces in the B-stage state of curable resin compositions. For example, in the examples described later, although there is no significant difference in glossiness between Example 3 and Comparative Example 2, the Rz of the former is less than half that of the latter. This is thought to be because the evaluation targets for glossiness and Rz are strictly different. The present invention was completed by taking into account that the evaluation targets for these parameters are different, and by finding that when their ratio is within a specific range, it exhibits excellent transferability when used as an adhesive film.

[0037] Thermosetting resin (A) The thermosetting resin (A) is not particularly limited, but examples include resins having reactive functional groups such as epoxy resins, maleimide resins, polyimide compounds, polyphenylene ether resins, siloxane compounds, and (meth)acrylate compounds. Among these, epoxy resins are preferred from the viewpoint of electrical insulation and heat resistance. One type of thermosetting resin (A) can be used alone, or two or more types can be used in combination.

[0038] Examples of epoxy resins include bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin; bixylenol type epoxy resin, cyclohexane type epoxy resin, dicyclopentadiene type epoxy resin, trisphenolmethane 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, and anthracene type epoxy resin. Examples include resins, oxazolidone ring-containing epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylmethane-type epoxy resins, aminophenol-type epoxy resins, and silicone-modified epoxy resins.

[0039] Among these, it is preferable that the curable resin composition contains at least one epoxy resin selected from the group consisting of aminophenol-type epoxy resins, bisphenol-type epoxy resins, and trisphenolmethane-type epoxy resins.

[0040] The number of epoxy groups in the epoxy resin is not particularly limited as long as it is one or more, but it is preferable that it be two or more (i.e., a polyfunctional epoxy resin). The epoxy resin may be liquid or solid at room temperature (25°C), but it is preferable that it be solid from the viewpoint of moldability into a film. In other words, it is preferable that the above curable resin composition contains a solid epoxy resin as the thermosetting resin (A).

[0041] Specific examples of liquid epoxy resins include "YDF-8170" and "YDF870GS" (both bisphenol F type epoxy resins), "YDF-8125" (bisphenol A type epoxy resin), "ZX-1658" and "ZX-1658GS" (both liquid 1,4-glycidylcyclohexane) from Nippon Steel Chemical & Material Co., Ltd.; "HP-4032," "HP-4032D," and "HP-4032SS" (all naphthalene type epoxy resins) from DIC Corporation; "Epiclon 830S" (bisphenol F type epoxy resin) from DIC Corporation; and "jER828US" and "jER828EL" (both bisphenol A type epoxy resins) from Mitsubishi Chemical Corporation. (Nol A type epoxy resin), "jER806", "jER807" (both bisphenol F type epoxy resins), "jER152" (phenol novolac type epoxy resin), "jER630", "jER630LSD" (both aminophenol type epoxy resins), "YX7400N" (aliphatic epoxy resin / diglycidyl ether of polytetramethylene glycol); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) and "EX-171" (lauryl alcohol (EO) manufactured by Nagase ChemteX Corporation) １５ Examples include glycidyl ether; "ADEKARESIN EP4005" (bisphenol A type epoxy resin containing polypropylene glycol structure), "EP-3950L" (aminophenol type epoxy resin), and "EP3980S" (glycidylamine type epoxy resin) from ADEKA Corporation; "AER9000" (PO-modified bisphenol type epoxy resin), "AER4001", "AER4004", and "AER4152" (all oxazolidone ring-containing epoxy resins) from Asahi Kasei Corporation; "DER852" and "DER858" (both oxazolidone ring-containing epoxy resins) from Dow Chemical Ltd; "FAE-2500" and "EPPN-501HY" (both trisphenolmethane type epoxy resins) from Nippon Kayaku Co., Ltd.; and "Celoxide 2021P" (alicyclic epoxy resin) from Daicel Corporation.

[0042] Specific examples of solid epoxy resins include "HP-4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both naphthalene-type tetrafunctional epoxy resins), "N-690" (cresol novolac-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", and "HP-7200HHH" (all DIC-type epoxy resins) manufactured by DIC Corporation. Lopentadiene-type epoxy resin), "EXA850CRP", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (all naphthylene ether-type epoxy resins); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenolmethane-type epoxy resin), "NC-7000-L" (naphthol novolac-type epoxy resin), "NC-3000-H", "NC-3000", "NC-3000- L, NC-3100 (both biphenyl-type epoxy resins); ESN475V (naphthol-type epoxy resin) and ESN485 (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; YX4000H, YL6121 (both biphenyl-type epoxy resins), YX4000HK (bixylenol-type epoxy resin), YL7760 (bisphenol AF-type epoxy resin), and YX8800 manufactured by Mitsubishi Chemical Corporation. Examples include (anthracene-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin), "jER157S70" (bisphenol novolac-type epoxy resin), "jER4005P", "jER4010P" (both bisphenol F-type epoxy resins); and "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.

[0043] As maleimide resins, compounds having one or more maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl groups) can be used. Examples include 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)ether, N,N'-ethylenedimaleimide, N,N'-hexamethylenedimaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, and other resins having two maleimide groups in the molecule, as well as biphenylaralkyl maleimide and polyphenylmethanemaleimide, and other resins having three or more maleimide groups in the molecule.

[0044] The polyimide compound has structural units derived from a maleimide compound having at least two N-substituted maleimide groups and structural units derived from a diamine compound. The above maleimide compound is not particularly limited, but examples include bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl'-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, and the like.The diamine compound is not particularly limited, and examples include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis{1-[4-(4-aminophenoxy)phenyl]-1-methylethyl}benzene, 1,4-bis{1-[4-(4-aminophenoxy)phenyl]-1-methylethyl}benzene, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene, and the like.

[0045] Examples of polyphenylene ether resins include resins having a functional group containing a carbon-carbon double bond at its terminal end and a polyphenylene ether backbone. Examples of functional groups containing a carbon-carbon double bond include (meth)acryloyl groups, vinyl groups, and vinylene groups. Commercially available polyphenylene ether resins include "OPE-2St 1200" and "OPE-2St 2200" (both vinyl benzyl-modified polyphenylene ether resins) from Mitsubishi Gas Chemical Company, Inc., and "Noryl SA9000" (methacrylic-modified polyphenylene ether resin) from SABIC Innovative Plastics Co., Ltd.

[0046] The siloxane compound is not particularly limited as long as it is a siloxane compound having a reactive functional group. The siloxane compound may be a linear polysiloxane compound or a branched polysiloxane compound. Examples of reactive functional groups that the siloxane compound may have include epoxy groups, amino groups, vinyl groups, hydroxyl groups, (meth)acrylic groups, mercapto groups, carboxyl groups, alkoxy groups, silanol groups, and the like.

[0047] Examples of the (meth)acrylate compound include monofunctional (meth)acrylate compounds and polyfunctional (meth)acrylate compounds. Examples of the monofunctional (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, diglycidyl (meth)acrylate, and the like. Examples of the polyfunctional (meth)acrylate compound include di(meth)acrylate of bisphenol A (or a PEGylated product thereof), di(meth)acrylate of dimethyloltricyclodecane, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, tri(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, tri(meth)acrylate of trimethylolpropane or oligomers thereof, poly(meth)acrylate of ditrimethylolpropane, tri(meth)acrylate of pentaerythritol or oligomers thereof, poly(meth)acrylate of dipentaerythritol, and polyester acrylate.

[0048] From the viewpoint of improving the flexibility of a cured product and reducing warpage, the curable resin composition of the present invention preferably contains a compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure; however, it is preferably not contained from the viewpoint that hygroscopicity increases and moisture resistance reliability tends to decrease.

[0049] In the compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure, examples of the radically polymerizable unsaturated group include groups containing an ethylenic carbon-carbon double bond, and specific examples thereof include a (meth)acryloyl group. Specific examples of the polyalkylene oxide structure include a polyethylene oxide structure and a polypropylene oxide structure.

[0050] Specific examples of compounds having a radically polymerizable unsaturated group and a polyalkylene oxide structure include "M-130G" (a compound having a methacryloyl group and a polyethylene oxide structure), "M-230G" (a compound having a methacryloyl group and a polyethylene oxide structure), "23G" (a compound having a methacryloyl group and a polyethylene oxide structure), "M-90G" (a compound having a methacryloyl group and a polyethylene oxide structure), "M-40G" (a compound having a methacryloyl group and a polyethylene oxide structure), "BPE-1300N" (a compound having a methacryloyl group and a polyethylene oxide structure), and "BPE-500" (a compound having a methacryloyl group and a polyethylene oxide structure), all manufactured by Shin Nakamura Chemical Industry Co., Ltd.

[0051] The content of thermosetting resin (A) in the above curable resin composition (100% by mass) is not particularly limited, but is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more. Alternatively, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. Alternatively, it is preferably 3 to 50% by mass, more preferably 6 to 40% by mass, even more preferably 8 to 30% by mass, and particularly preferably 10 to 25% by mass. When the content of thermosetting resin (A) is within the above range, excellent laminating properties (adhesion) tend to be exhibited.

[0052] The content of thermosetting resin (A) relative to the nonvolatile content (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 8% by mass or more, even more preferably 10% by mass or more, and particularly preferably 12% by mass or more. Also, is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 36% by mass or less, and particularly preferably 32% by mass or less. Also, is preferably 3 to 60% by mass, more preferably 6 to 50% by mass, even more preferably 8 to 40% by mass, even more preferably 10 to 36% by mass, and particularly preferably 12 to 32% by mass. When the content of thermosetting resin (A) is within the above range, excellent laminating properties (adhesion) tend to be exhibited.

[0053] In this specification, non-volatile components refer to components that remain without volatilizing after the curable resin composition has been subjected to treatment such as heating or reduced pressure. Examples include thermosetting resin (A), curing agent (B1), curing accelerator (B2), inorganic filler (C), silane coupling agent (D), and other components (E).

[0054] The epoxy resin content relative to the thermosetting resin (A) (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. When the epoxy resin content is within the above range, the transferability of the above curable resin composition tends to be further improved.

[0055] The content of the compound having a radical polymerizable unsaturated group and a polyalkylene oxide structure in the above curable resin composition relative to the thermosetting resin (A) (100% by mass) is not particularly limited, but is preferably 32% by mass or less, more preferably 16% by mass or less, even more preferably 8% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, and most preferably substantially absent. When the content of the compound having a radical polymerizable unsaturated group and a polyalkylene oxide structure is within the above range, the transferability of the above curable resin composition tends to be further improved.

[0056] When the above curable resin composition contains an epoxy resin, the content of solid epoxy resin relative to the epoxy resin (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more. Alternatively, it may be 90% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less. When the content of solid epoxy resin is within the above range, the film moldability of the above curable resin composition tends to improve. Furthermore, the transferability of the above curable resin composition tends to improve.

[0057] • Curing agent (B1) The above curable resin composition may contain a curing agent (B1). The curing agent (B1) is not particularly limited as long as it is used as a curing agent for thermosetting resins, but examples include amine-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, active ester-based curing agents, and dicyandiamide. One type of curing agent (B1) may be used alone, or two or more types may be used in combination.

[0058] Examples of amine-based curing agents include aromatic amines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine, methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone.

[0059] Examples of acid anhydride-based curing agents include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methylnadoic anhydride.

[0060] Examples of phenolic curing agents include phenol novolac resins, cresol novolac resins, naphthol-modified phenolic resins, dicyclopentadiene-modified phenolic resins, and p-xylene-modified phenolic resins.

[0061] Examples of active ester curing agents include compounds that have highly reactive ester groups and exhibit a curing effect on thermosetting resins (particularly epoxy resins), such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having two or more active ester groups in a single molecule are preferred as active ester curing agents.

[0062] The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Examples of the carboxylic acid compound include aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid, and aliphatic carboxylic acids such as acetic acid, succinic acid, maleic acid, and itaconic acid. Examples of thiocarboxylic acid compounds include thioacetic acid and thiobenzoic acid. Examples of the hydroxy compounds mentioned above include phenol compounds or naphthol compounds such as bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, hydroquinone, resorcinol, phenolphthalein, phenol novolac, phloroglucin, benzenetriol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. Examples of the thiol compounds mentioned above include benzenedithiol and triazinedithiol.

[0063] Furthermore, in the above curable resin composition, from the viewpoint of adhesion and insulation, it is preferable that catechol resorcinol novolac resin is included as the curing agent (B1). On the other hand, from the viewpoint of high hygroscopicity, it is preferable that catechol resorcinol novolac resin is not included.

[0064] The content of the curing agent (B1) relative to the above curable resin composition (100% by mass) is not particularly limited, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more. Also, is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less. Also, is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, even more preferably 0.2 to 5% by mass, even more preferably 0.3 to 3% by mass, and particularly preferably 0.3 to 2% by mass. When the content of the curing agent (B1) is within the above range, the curability of the above curable resin composition tends to improve.

[0065] The content of the curing agent (B1) in the above curable resin composition relative to the nonvolatile content (100% by mass) is not particularly limited, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more. Also, is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less. Also, is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, even more preferably 0.2 to 5% by mass, even more preferably 0.3 to 3% by mass, and particularly preferably 0.3 to 2% by mass. When the content of the curing agent (B1) is within the above range, the curability of the above curable resin composition tends to improve.

[0066] The content of the curing agent (B1) relative to the thermosetting resin (A) (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more. Also, is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, even more preferably 10% by mass or less, even more preferably 8% by mass or less, even more preferably 6% by mass or less, and particularly preferably 5% by mass or less. Also, is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, and particularly preferably 2 to 5% by mass. When the content of the curing agent (B1) is within the above range, the curability of the above curable resin composition tends to improve.

[0067] • Curing accelerator (B2) The above curable resin composition may contain a curing accelerator (B2). The curing accelerator (B2) is not particularly limited as long as it is used to accelerate the curing of the thermosetting resin, but examples include imidazole-based curing accelerators, tertiary amine-based curing accelerators, and phosphorus-based curing accelerators. The curing accelerator (B2) can be used alone or in combination of two or more types.

[0068] Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine. Commercially available products include 2-ethyl-4-methylimidazole (product name "2E4MZ"), 2-phenyl-4-methylimidazole (product name "2P4MZ"), 2-phenyl-4-methyl-5-hydroxymethylimidazole (product name "2P4MHZ-PW"), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (product name "2MZA-PW"), "2MZ-OK", "2MA-OK", and "2PHZ", all manufactured by Shikoku Chemicals, Inc. In addition, encapsulated imidazoles, such as microencapsulated imidazoles and epoxy adduct imidazoles, may also be used. Commercially available products include "HX3941HP", "HXA3942HP", "HXA3922HP", "HXA3792", "HX3748", "HX3721", "HX3722", "HX3088", "HX3741", "HX3742", and "HX3613" (all manufactured by Asahi Kasei Corporation), as well as "PN-23J", "PN-40J", and "PN-50" (manufactured by Ajinomoto Fine Techno Co., Ltd.), and "FXR-1121" (manufactured by Fuji Kasei Kogyo Co., Ltd.).

[0069] Examples of tertiary amine-based curing accelerators include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N'-dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene, 1,5-diazabicyclo[4.3.0]nonene, and salts thereof. Examples of the salts include formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, or phenol novolac resin salt of 1,8-diazabicyclo[5.4.0]undecene, and formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, or phenol novolac resin salt of 1,5-diazabicyclo[4.3.0]nonene.

[0070] Examples of phosphorus-based curing accelerators include phosphorus compounds such as triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium / tetraphenylborate, triphenylphosphine / triphenylborane, and 1,2-bis-(diphenylphosphine)ethane.

[0071] The content of the curing accelerator (B2) in the above curable resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.04% by mass or more, and particularly preferably 0.06% by mass or more. Also, is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.6% by mass or less, and particularly preferably 0.3% by mass or less. Also, is preferably 0.01 to 3% by mass, more preferably 0.02 to 1% by mass, even more preferably 0.04 to 0.6% by mass, and particularly preferably 0.06 to 0.3% by mass. When the content of the curing accelerator (B2) is within the above range, the curability of the above curable resin composition tends to improve.

[0072] The content of the curing accelerator (B2) in the above curable resin composition relative to the nonvolatile content (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.04% by mass or more, and particularly preferably 0.06% by mass or more. Also, is preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.6% by mass or less, and particularly preferably 0.3% by mass or less. Also, is preferably 0.01 to 3% by mass, more preferably 0.02 to 1% by mass, even more preferably 0.04 to 0.6% by mass, and particularly preferably 0.06 to 0.3% by mass. When the content of the curing accelerator (B2) is within the above range, the curability of the above curable resin composition tends to improve.

[0073] The content of the curing accelerator (B2) relative to the thermosetting resin (A) (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. Also, is preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. Also, is preferably 0.01 to 4% by mass, more preferably 0.05 to 3% by mass, even more preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass. When the content of the curing accelerator (B2) is within the above range, the curability of the above curable resin composition tends to improve.

[0074] • Inorganic filler (C) The inorganic filler (C) is not particularly limited, but examples include silica (silicon dioxide), silicon carbide, silicon nitride, alumina (aluminum oxide), aluminum nitride, aluminum hydroxide, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, barium sulfate, barium carbonate, titanium oxide, lime sulfate, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and materials with treated surfaces (surface-treated materials). Among these, from the viewpoint of transferability, the above curable resin composition preferably contains at least one selected from the group consisting of silica, alumina, and materials with treated surfaces, and preferably contains alumina or materials with treated surfaces. One type of inorganic filler (C) can be used alone, or two or more types can be used in combination.

[0075] Examples of inorganic fillers (C) include inorganic fillers (C1) whose surface has not been treated, and inorganic fillers (C2) whose surface has been modified with a silane coupling agent.

[0076] Examples of silane coupling agents in the inorganic filler (C2) include those exemplified as silane coupling agent (D) described later. Among these, silane coupling agents having a (meth)acryloyl group or an amino group (particularly a phenylamino group) are preferred from the viewpoint of transferability (especially peelability from the substrate). Examples of the above silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 8-phenylaminooctyltrimethoxysilane. One of the above silane coupling agents can be used alone for surface treatment of the inorganic filler (C2), or two or more can be used in combination.

[0077] Inorganic filler (C) (especially inorganic filler (C1)) tends to improve the transferability of the adhesive film when combined with the silane coupling agent (D) described later and incorporated into the curable resin composition. Furthermore, inorganic filler (C2) also tends to improve the transferability of the adhesive film when incorporated into the curable resin composition. Comparing the former and the latter, the former tends to improve transferability more significantly. This is thought to be because when the silane coupling agent (D) is incorporated into the curable resin composition as a single component, the value of the maximum height roughness Rz of the adhesive film decreases, making it easier for the G / R value in formula (1) to be 160 or higher.

[0078] The shape of the inorganic filler (C) is not particularly limited, but examples include spherical (perfectly spherical, nearly spherical, etc.), polyhedral, rod-shaped (cylindrical, prismatic, etc.), plate-shaped, flake-shaped, and irregularly shaped. Among these, a spherical shape is preferred from the viewpoint of achieving a high filling capacity.

[0079] The average particle size of the inorganic filler (C) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.05 to 10 μm, even more preferably 0.1 to 6 μm, even more preferably 0.2 to 5 μm, even more preferably 0.3 to 4 μm, even more preferably 0.4 to 4 μm, and particularly preferably 0.5 to 4 μm. In particular, the above curable resin composition preferably contains 60% by mass or more of inorganic filler with an average particle size of 0.5 μm or more (especially 0.5 to 5 μm) relative to the inorganic filler (C) (100% by mass), more preferably 75% by mass or more, and even more preferably 90% by mass or more. When the content of inorganic filler with an average particle size of 0.5 μm or more is within the above range, adhesion and film-forming properties tend to improve.

[0080] In this specification, unless otherwise specified, the average particle size of the inorganic filler (C) refers to the volume-based median diameter (D50) measured by laser diffraction scattering in accordance with ISO-13320 (2020). The average particle size of the inorganic filler (C) can be measured, for example, using a laser diffraction scattering particle size distribution analyzer (product name: LS 13 320, manufactured by Beckman Coulter, Inc.).

[0081] The content of inorganic filler (C) in the above curable resin composition (100% by mass) is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and particularly preferably 50% by mass or more. Also, is preferably 84% by mass or less, more preferably 80% by mass or less, even more preferably 76% by mass or less, and particularly preferably 72% by mass or less. Also, is preferably 30 to 84% by mass, more preferably 40 to 80% by mass, even more preferably 45 to 76% by mass, and particularly preferably 50 to 72% by mass. When the content of inorganic filler (C) is within the above range, the adhesive film tends to exhibit excellent transferability.

[0082] The content of inorganic filler (C) relative to nonvolatile matter (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, even more preferably 60% by mass or more, and particularly preferably 65% ​​by mass or more. Also, is preferably 92% by mass or less, more preferably 90% by mass or less, even more preferably 88% by mass or less, and particularly preferably 86% by mass or less. Also, is preferably 40 to 92% by mass, more preferably 50 to 90% by mass, even more preferably 55 to 88% by mass, even more preferably 60 to 86% by mass, and particularly preferably 65 to 86% by mass. When the content of inorganic filler (C) is within the above range, the adhesive film tends to exhibit excellent transferability.

[0083] The content of inorganic filler (C) relative to thermosetting resin (A) (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 150% by mass or more, more preferably 180% by mass or more, even more preferably 200% by mass or more, even more preferably 210% by mass or more, and particularly preferably 220% by mass or more. Also, is preferably 1000% by mass or less, more preferably 800% by mass or less, even more preferably 750% by mass or less, even more preferably 700% by mass or less, and particularly preferably 650% by mass or less. Also, is preferably 150 to 1000% by mass, more preferably 180 to 800% by mass, even more preferably 200 to 750% by mass, even more preferably 210 to 700% by mass, and particularly preferably 220 to 650% by mass. When the content of inorganic filler (C) is within the above range, the adhesive film tends to exhibit excellent transferability.

[0084] The content of inorganic filler (C1) relative to inorganic filler (C) (100% by mass) in the above curable resin composition is not particularly limited, but for example it is 5% by mass or more, 10% by mass or more, 30% by mass or more, 50% by mass or more, or 80% by mass or more. Also, for example it is 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. Also, for example it is 5 to 90% by mass, 10 to 80% by mass, 30 to 70% by mass, or 50 to 60% by mass. The content of inorganic filler (C2) relative to inorganic filler (C) (100% by mass) in the above curable resin composition is not particularly limited, but for example it is 5% by mass or more, 10% by mass or more, 30% by mass or more, or 50% by mass or more. Also, for example it is 90% by mass or less, 50% by mass or less, 30% by mass or less, 10% by mass or less, or 1% by mass or less. For example, these range from 5-90% by mass, 5-50% by mass, 5-30% by mass, and 5-10% by mass.

[0085] Silane coupling agent (D) The silane coupling agent (D) is not particularly limited, but examples include silane coupling agents having reactive functional groups such as vinyl groups, epoxy groups, styryl groups, (meth)acryloyl groups, amino groups (e.g., phenylamino groups), isocyanurate groups, ureido groups, mercapto groups, sulfide groups, and isocyanate groups. One type of silane coupling agent (D) can be used alone, or two or more types can be used in combination.

[0086] Examples of the silane coupling agent (D) include silane coupling agents having epoxy groups such as 3-glycidyloxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; silane coupling agents having (meth)acryloyl groups such as 3-methacryloxypropyltrimethoxysilane and 8-methacryloxyoctyltrimethoxysilane; silane coupling agents having amino groups (especially phenylamino groups) such as N-phenyl-3-aminopropyltrimethoxysilane and 8-phenylaminooctyltrimethoxysilane; and silane coupling agents having ureido groups such as 3-ureidopropyltriethoxysilane. Among these, from the viewpoint of the transferability of the adhesive film (especially its peelability from the substrate), it is preferable that the silane coupling agent (D) is a silane coupling agent having a phenylamino group.

[0087] Specific examples of silane coupling agents (D) include, for example, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-5803, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, KBM-575, KBM-802, KBM-803 (product names, all manufactured by Shin-Etsu Chemical Co., Ltd.), A-189, and A-1160 (product names, all manufactured by Momentive Performance Materials Japan LLC).

[0088] The content of the silane coupling agent (D) in the above curable resin composition (100% by mass) is not particularly limited, but is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, and particularly preferably 0.03% by mass or more. Also, is preferably 2% by mass or less, more preferably 1.6% by mass or less, even more preferably 1.2% by mass or less, and particularly preferably 1% by mass or less. Also, is preferably 0.005 to 2% by mass, more preferably 0.01 to 1.6% by mass, even more preferably 0.02 to 1.2% by mass, and particularly preferably 0.03 to 1% by mass. When the content of the silane coupling agent (D) is within the above range, the adhesive film tends to exhibit better transferability (especially peelability from the substrate).

[0089] The content of the silane coupling agent (D) in the above curable resin composition relative to the nonvolatile content (100% by mass) is not particularly limited, but is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, and particularly preferably 0.03% by mass or more. Also, is preferably 2% by mass or less, more preferably 1.6% by mass or less, even more preferably 1.2% by mass or less, and particularly preferably 1% by mass or less. Also, is preferably 0.005 to 2% by mass, more preferably 0.01 to 1.6% by mass, even more preferably 0.02 to 1.2% by mass, and particularly preferably 0.03 to 1% by mass. When the content of the silane coupling agent (D) is within the above range, the adhesive film tends to exhibit better transferability (especially peelability from the substrate).

[0090] The content of the silane coupling agent (D) relative to the thermosetting resin (A) (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 0.03% by mass or more, more preferably 0.06% by mass or more, even more preferably 0.09% by mass or more, even more preferably 0.12% by mass or more, and particularly preferably 0.15% by mass or more. Also, is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. Also, is preferably 0.03 to 30% by mass, more preferably 0.06 to 20% by mass, even more preferably 0.09 to 15% by mass, even more preferably 0.12 to 15% by mass, and particularly preferably 0.15 to 10% by mass. When the content of the silane coupling agent (D) is within the above range, the adhesive film tends to exhibit better transferability (especially peelability from the substrate).

[0091] The content of the silane coupling agent (D) relative to the inorganic filler (C) (100% by mass) in the above curable resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, even more preferably 0.03% by mass or more, even more preferably 0.04% by mass or more, and particularly preferably 0.05% by mass or more. Also, is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less. Also, is preferably 0.01 to 5% by mass, more preferably 0.02 to 4% by mass, even more preferably 0.03 to 3% by mass, even more preferably 0.04 to 2% by mass, and particularly preferably 0.05 to 1.5% by mass. When the content of the silane coupling agent (D) is within the above range, the adhesive film tends to exhibit better transferability (especially peelability from the substrate).

[0092] Other Components (E) The curable resin composition of the present invention may or may not contain components other than the thermosetting resin (A), curing agent (B1), curing accelerator (B2), inorganic filler (C), silane coupling agent (D), and solvent (F) described below (hereinafter referred to as "other components (E)"). Examples of other components (E) include thermoplastic resins (e.g., phenoxy resin, polyvinyl acetal resin, polyphenylene ether resin), elastomers (e.g., core-shell rubber particles, acrylic copolymer), surfactants, ion trapping agents, leveling agents, antioxidants, defoaming agents, flame retardants, colorants such as carbon black, reactive diluents, radical generators, etc. One type of other component (E) may be used alone, or two or more types may be used in combination.

[0093] From the viewpoint of improving the impact resistance and flexibility of the cured product, the above curable resin composition preferably contains phenoxy resin (a resin having a phenoxy structure), but from the viewpoint of improving the heat resistance of the cured product, it is preferable not to include it.

[0094] The above curable resin composition preferably includes a radical generator if it contains a radical-curable resin, but it does not need to contain one if it does not contain a radical-curable resin, as this may adversely affect the curability of other thermosetting resins.

[0095] The content of other components (E) relative to the above curable resin composition (100% by mass) is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. Also, for example, it is 0.01% by mass or more. Also, for example, it is 0.01 to 10% by mass, 0.01 to 5% by mass, 0.01 to 3% by mass, 0.01 to 1% by mass, and 0.01 to 0.1% by mass.

[0096] The content of other components (E) relative to the nonvolatile content (100% by mass) in the above curable resin composition is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. Also, for example, it is 0.01% by mass or more. Also, for example, it is 0.01 to 10% by mass, 0.01 to 5% by mass, 0.01 to 3% by mass, 0.01 to 1% by mass, and 0.01 to 0.1% by mass.

[0097] • Solvent (F) The above curable resin composition may contain a solvent (F). Examples of solvents (F) include glycol-based solvents such as propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ether-based solvents such as 1,4-dioxane, tetrahydrofuran, and anisole; aromatic solvents such as toluene; and ester-based solvents such as ethyl acetate.

[0098] The content of solvent (F) in the above curable resin composition (100% by mass) is not particularly limited, but is preferably 4% by mass or more, more preferably 8% by mass or more, even more preferably 12% by mass or more, and particularly preferably 15% by mass or more. Also, is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 18% by mass or less. Also, is preferably 4 to 30% by mass, more preferably 8 to 25% by mass, even more preferably 12 to 20% by mass, and particularly preferably 15 to 18% by mass.

[0099] (Physical properties and manufacturing method of curable resin composition) The viscosity of the above curable resin composition at 25°C at 1 rpm is not particularly limited, but is preferably 30 to 1500 Pa·s, more preferably 60 to 1200 Pa·s, and even more preferably 90 to 900 Pa·s. The viscosity of the above curable resin composition at 25°C at 10 rpm is also not particularly limited, but is preferably 30 to 2000 Pa·s, more preferably 60 to 1500 Pa·s, even more preferably 90 to 1200 Pa·s, and especially preferably 120 to 1000 Pa·s. Having a viscosity within the above range allows for good handling when forming the curable resin composition into a film.

[0100] The TI value (thixotropic index, 1 rpm / 10 rpm) of the above curable resin composition at 25°C is not particularly limited, but is preferably 0.5 to 1.5, more preferably 0.6 to 1.4, and even more preferably 0.65 to 1.3. Having a TI value within this range allows for good handling when forming the curable resin composition into a film.

[0101] The viscosity described above can be measured using a TVE-25 viscometer (model number: TVE-25L or TVE-25H, rotor: 1°34' × R24 (rotor code 01), manufactured by Toki Sangyo Co., Ltd.) with the curable resin composition at a liquid temperature of 25°C, and measured as the viscosity when rotated at 1 rpm and 10 rpm for 1 minute. The TI value can be calculated using the following formula: TI value (1 rpm / 10 rpm) = viscosity at 1 rpm (Pa·s) / viscosity at 10 rpm (Pa·s). More specifically, the viscosity and TI value described above can be measured and calculated by the method explained in the examples below.

[0102] The above-mentioned curable resin composition can be prepared by known and conventional methods. For example, the above-mentioned curable resin composition can be obtained by introducing components such as thermosetting resin (A) simultaneously or separately into a suitable mixer, and stirring and mixing them while melting them by heating as needed.

[0103] The above-mentioned mixer is not particularly limited, but examples include a roll mill equipped with a stirring device and a heating device, a Leikai machine, a Henschel mixer, a tumbler, a self-rotating mill, a planetary mixer, etc. The mixing ratio of each component is appropriately set according to the content ratio of each component in the curable resin composition.

[0104] [Adhesive Film] The adhesive film of the present invention uses the above-mentioned curable resin composition. Specifically, the adhesive film is a film formed by heating and drying the above-mentioned curable resin composition. In the production of the adhesive film, components such as a thermosetting resin (A) are mixed in a solvent (F) to form a varnish-like curable resin composition, which is then applied to a substrate such as a PET film using a flow coater, roll coater, comma coater, etc., and the solvent (F) is removed by heating and drying to produce the adhesive film. The heating and drying conditions are not particularly limited, but for example, they are 60 to 120°C for 1 to 60 minutes. In the examples described later, the curable resin composition was coated onto the surface of a substrate and dried at 100°C for 10 minutes to reach the B-stage state, but this B-stage state curable resin composition is also included in the adhesive film.

[0105] [Laminated Sheet] The laminated sheet of the present invention is characterized by comprising the above-mentioned adhesive film and a substrate. The substrate in the above-mentioned laminated sheet may be a laminate of two or more substrates. The substrate used for the laminated sheet is not particularly limited, but examples include polyester, polytetrafluoroethylene, polyethylene (PE), polypropylene, polymethylpentene, polyvinyl chloride (PVC), polyethylene terephthalate (PET), and polyolefin (PO). The surface of the above-mentioned substrate may or may not be peel-treated. If the surface of the above-mentioned substrate is peel-treated, it may be peel-treated with a silicone-based peel-treatment agent or with a non-silicone-based peel-treatment agent.

[0106] The contact angle with pure water on the surface of the above substrate is not particularly limited, but for example, it is 70 to 120°. The 31B tape peel strength on the peeled surface of the above substrate is not particularly limited, but for example, it is preferably 100 mN / 25 mm or more, more preferably 300 mN / 25 mm or more, even more preferably 500 mN / 25 mm or more, even more preferably 1000 mN / 25 mm or more, even more preferably 1500 mN / 25 mm or more, and particularly preferably 2000 mN / 25 mm or more. The upper limit is 4500 mN / 25 mm (i.e., 4500 mN / 25 mm or less). The laminated sheet of the present invention exhibits excellent transferability even when the 31B tape peel strength on the peeled surface of the above substrate is high. Furthermore, because a substrate with high 31B tape peel strength can be used, when forming an adhesive film, the curable resin composition and the substrate surface adhere well, and repulsion is suppressed, making it easy to form an adhesive film. Here, "31B tape peel strength" refers to the peel strength when 31B tape (manufactured by Nitto Denko, substrate thickness 25 μm) is applied to the side of the substrate where the adhesive film is placed, and then peeled off at a peel speed of 300 mm / min and a peel angle of 180°.

[0107] The laminated sheet of the present invention is preferably used as a laminated sheet for semiconductors (for use in semiconductor devices), as described below, and is particularly preferably used for applications where it is disposed on a semiconductor element or substrate. Specifically, the laminated sheet (film) of the present invention can be used, for example, as a die attach film for bonding a semiconductor element to a substrate, a die attach film for laminating multiple semiconductor elements, a heat dissipation film for efficiently releasing heat from a semiconductor element, a sealing film for sealing a semiconductor element, an insulating protective film for protecting the surface of a semiconductor element, and the like.

[0108] The laminated sheet of the present invention preferably further comprises a release film on the adhesive film. The laminated sheet comprising the release film is referred to as a "laminated sheet with release film." That is, a laminated sheet with release film is formed by laminating a release film, an adhesive film, and a substrate in this order. The material of the release film is the same as that of the substrate, and includes, for example, polyester, polytetrafluoroethylene, polyethylene (PE), polypropylene, polymethylpentene, polyvinyl chloride (PVC), polyethylene terephthalate (PET), and polyolefin (PO). The surface of the release film may or may not be treated for release.

[0109] [Cured product] The cured product of the present invention is formed by performing a heat treatment on the adhesive film. The heat treatment conditions are, for example, 60 to 200°C for 0.1 to 5 hours.

[0110] [Semiconductor device and method for manufacturing the same] The semiconductor device of the present invention is manufactured using the adhesive film described above. The method for manufacturing the semiconductor device is described below. First, the release film is removed from the laminated sheet with the release film to prepare the laminated sheet. The adhesive film is in the form of a laminated sheet and is laminated (pressed) onto a semiconductor substrate such as a glass carrier substrate or a semiconductor wafer to form a laminate consisting of the laminated sheet and the substrate. In other words, the adhesive film is used to laminate the semiconductor substrate. In this laminate, the substrate, adhesive film, and semiconductor substrate are laminated in this order. Next, the substrate is peeled off from the laminate to expose the surface of the adhesive film, and the semiconductor substrate or semiconductor element is joined via the adhesive film. When joining the semiconductor substrate and the semiconductor element, the adhesive film functions as an insulating adhesive layer and also functions as a sealant that fills the gap between the semiconductor element and the semiconductor substrate. The semiconductor substrates joined together, or the semiconductor substrate and the semiconductor element, via the adhesive film are heated to cure the adhesive film. As a result, a semiconductor device including the cured adhesive film and a semiconductor element and / or semiconductor substrate is formed.

[0111] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0112] The curable resin compositions of the examples and comparative examples were prepared by dissolving and mixing components such as the thermosetting resin (A) in a solvent (F) to the proportions shown in Table 1. The numerical values ​​for each component in Table 1 represent parts by mass.

[0113] The following is a description of each component in Table 1. • Thermosetting resins (A) jER630 (product name): Aminophenol type epoxy resin, epoxy equivalent 90-106 g / eq, liquid at 25°C, manufactured by Mitsubishi Chemical Corporation Epiclon 830S (product name): Bisphenol F type epoxy resin, liquid at 25°C, epoxy equivalent 165-180 g / eq, manufactured by DIC Corporation RE410S (product name): Bisphenol A type epoxy resin, liquid at 25°C, epoxy equivalent 178 g / eq, manufactured by Nippon Kayaku Co., Ltd. jER4005P (product name): Bisphenol F type epoxy resin, solid at 25°C, epoxy equivalent 950-1200 g / eq, manufactured by Mitsubishi Chemical Corporation jER4010P (product name): Bisphenol F type epoxy resin, solid at 25°C, epoxy equivalent 3800-4600 g / eq, manufactured by Mitsubishi Chemical Corporation EPPN-502H (Product Name): Trisphenolmethane type epoxy resin, solid at 25°C (solid state), epoxy equivalent 168 g / eq, manufactured by Nippon Kayaku Co., Ltd., curing agent (B1) DICY7 (Product Name): Dicyandiamide, manufactured by Mitsubishi Chemical Corporation, curing accelerator (B2) 1B2PZ (Product Name): 1-benzyl-2-phenylimidazole, imidazole-based curing accelerator, manufactured by Shikoku Chemicals, Inc., inorganic filler (C) AX3 10 (Product Name): Untreated alumina filler, average particle size 3 μm, manufactured by Nippon Steel Chemical & Material Co., Ltd. A14-SX-C17 (Product Name): Alumina filler surface-treated with a silane coupling agent (phenylaminosilane) containing a phenylamino group, average particle size 3 μm, manufactured by Admatex Co., Ltd. ASFP 20 (Product Name): Untreated alumina filler, average particle size 0.3 μm, manufactured by Admatex Co., Ltd. SC4050 SX (Product Name): Silica filler surface-treated with a silane coupling agent (phenylaminosilane) containing a phenylamino group, average particle size 1.1 μm, manufactured by Admatex Co., Ltd. SC4053-SQ (Product Name): Untreated silica filler, average particle size 1.1 μm, manufactured by Admatex Co., Ltd., silane coupling agent (D) KBM-573 (Product Name): N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.KBM-503 (product name): 3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. KBM-403 (product name): 3-glycidyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Other (E) Black 4: Product name "Special Black 4 powder", colorant, manufactured by Orion Engineered Carbons Co., Ltd. MMGAC: ethylene glycol monomethyl ether acetate, solvent MIBK: methyl isobutyl ketone, solvent

[0114] (Evaluation 1: Measurement of Viscosity and TI Value) The viscosity (Pa·s) and TI value (thixotropic index, 1 rpm / 10 rpm) of the curable resin compositions of the examples and comparative examples at 25°C were measured and calculated. Specifically, a TVE-25 viscometer (model number: TVE-25L or TVE-25H, rotor: 1°34' × R24 (rotor code 01), manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity (referred to as 1 rpm viscosity and 10 rpm viscosity, respectively) when the curable resin composition was rotated at 1 rpm and 10 rpm for 1 minute, with the liquid temperature of the curable resin composition set to 25°C, and the TI value was calculated from the following formula. TVE-25L was used when the viscosity was less than 1 Pa·s, and TVE-25H was used when the viscosity was 1 Pa·s or more. The TI value (1 rpm / 10 rpm) = viscosity at 1 rpm (Pa·s) / viscosity at 10 rpm (Pa·s). The results are recorded in Table 1 under "Viscosity at 1 rpm (Pa·s)", "Viscosity at 10 rpm (Pa·s)", and "TI value (1 rpm / 10 rpm)".

[0115] (Evaluation 2: Measurement of surface roughness) The curable resin compositions of the examples and comparative examples were coated onto the surface of a substrate (PET film with a non-silicone release treatment on its surface, pure contact angle: 102°, 31B tape peel strength: 124 mN / 25 mm, thickness: 25 μm) so that the thickness after drying was 30 to 60 μm, and dried at 100°C for 10 minutes to reach the B stage state. In other words, a laminated sheet consisting of a substrate and an adhesive film provided on one surface of the substrate was prepared by the above procedure.

[0116] The surface morphology of adhesive films was measured using a confocal scanning electron microscope OPTELICS H1200 (manufactured by Lasertec Corporation), and the arithmetic mean roughness Ra (μm) and maximum height roughness Rz (μm) were calculated according to the method specified in JIS B 0601:2013 (in accordance with the international standard ISO 4287-1997). The measurement conditions were as follows: scan width 100 μm, scan type area, light source Blue, cutoff value 1 / 5. The object lens was set to ×100, contact lens to ×14, digital zoom to ×1, and Z pitch to 10 nm. Data was acquired at three locations, and Ra and Rz were taken as the average values ​​of the three arbitrary locations. The results are listed in "Ra (μm)" and "Rz (μm)" in Table 1.

[0117] (Evaluation 3: Measurement of Glossiness) For the laminated sheets prepared in Evaluation 2, the glossiness (%) at an incident angle of 60° on the surface of the adhesive film was measured using a gloss meter (product name: Handy Gloss Meter PG-II, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS Z 8741:1997. The results are listed in "Glossiness (%)" in Table 1.

[0118] (Evaluation 4: Lamination Properties) The laminated sheet prepared in Evaluation 2 was evaluated for its lamination properties to the substrate. First, a PET film (PET film with a non-silicone release treatment on its surface, pure contact angle: 94°, 31B tape peel strength: 2313 mN / 25 mm, thickness: 38 μm) was bonded to the surface of the adhesive film in the laminated sheet as the substrate. Then, roll lamination was performed at 80°C and 0.3 m / min to create a laminate with a three-layer structure of PET film / adhesive film / substrate. The surface size of the adhesive film and PET film used was 10 cm vertically x 10 cm horizontally. The obtained laminate was folded 90 degrees so that the PET film was on the outside, then returned to a flat surface, and the "lifting" of the laminated PET film was visually observed. The presence or absence of lifting was determined by whether or not bubbles or air layers were formed at the interface between the adhesive film and the PET film. The same checks were performed at 10 arbitrary locations on the above laminate, and the number of PET film lifts was measured and evaluated according to the following criteria. The results are listed in "Laminating Properties" in Table 1. • Evaluation Criteria A: 0 lifts B: 1 lift C: 2-5 lifts D: 6-10 lifts

[0119] (Evaluation 5: Transferability) The curable resin compositions of the examples and comparative examples were coated onto the surfaces of the following substrates 1 to 3, and dried at 100°C for 10 minutes to reach the B stage, thereby producing laminated sheets of adhesive film and substrate. ・Substrate 1: PET film (substrate with non-silicone release treatment on the surface, pure contact angle: 102°, 31B tape peel strength: 124 mN / 25 mm) ・Substrate 2: PET film (substrate with non-silicone release treatment on the surface, pure contact angle: 96°, 31B tape peel strength: 688 mN / 25 mm) ・Substrate 3: PET film (substrate with non-silicone release treatment on the surface, pure contact angle: 94°, 31B tape peel strength: 2313 mN / 25 mm)

[0120] A laminate with a three-layer structure of copper foil / adhesive film / substrate was fabricated by laminating the glossy surface of copper foil (manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd., product name "CF-V9S-SV-18") with the surface of the adhesive film in the above laminate sheet in contact, and then roll laminating at 80°C and 0.3 m / min. The substrate was peeled off from the obtained laminate, and the transferability to the substrate was evaluated according to the following criteria. The results are shown in Table 2. ・Evaluation Criteria A: No peeling occurs at the interface between the copper foil and the adhesive film, only the substrate is peeled off, and no adhesive film remains on the peeled surface of the substrate. B: No peeling occurs at the interface between the copper foil and the adhesive film, only the substrate is peeled off, but some adhesive film remains on the peeled surface of the substrate. C: Peeling occurs at the interface between the copper foil and the adhesive film, or no peeling occurs at the interface between the copper foil and the adhesive film, only the substrate is peeled off, but adhesive film remains on the entire surface of the substrate.

[0121] As a result of Evaluation 5, it was confirmed that when the laminated sheets of the present invention (Examples 1 to 8) were laminated to a glossy substrate, peeling did not occur at the interface between the substrate and the adhesive film even when the substrate was peeled off, and only the substrate was peeled off, meaning that the transferability was excellent. On the other hand, it was confirmed that the laminated sheets of Comparative Examples 1 to 3 had inferior transferability, with problems such as adhesive film remaining on part or all of the peeled surface of the substrate during peeling, or peeling occurring at the interface between the copper foil and the adhesive film in the first place. From these results, it was demonstrated that the adhesive film formed from the curable resin composition of the present invention exhibits excellent laminating (adhesion) to glossy substrates while possessing excellent peelability to the substrate, thus demonstrating excellent transferability.

[0122]

[0123]

[0124] In summary, the configuration of the present invention and its variations are described below. [1] A curable resin composition comprising a thermosetting resin (A) and an inorganic filler (C), further comprising a silane coupling agent (D), or an inorganic filler (C2) modified with a silane coupling agent as the inorganic filler (C), wherein the curable resin composition satisfies the following formula (1). G / R ≥ 160 (1) (wherein G represents the gloss (%) at an incident angle of 60° in the B-stage state of the curable resin composition. R represents the maximum height roughness Rz (μm) in the B-stage state of the curable resin composition.) [2] The curable resin composition according to [1], wherein the gloss (%) at an incident angle of 60° in the B-stage state (i.e., G in formula (1)) is 50% or more, 60% or more, 70% or more, or 80% or more, and / or 140% or less, 130% or less, 120% or less, or 115% or less, or 50 to 140%, 60 to 130%, 70 to 120%, or 80 to 115%. [3] The curable resin composition according to [1] or [2], wherein the maximum height roughness Rz (μm) (i.e., R in formula (1)) in the B-stage state is 0.1 μm or more, 0.15 μm or more, 0.18 μm or more, 0.2 μm or more, or 0.22 μm or more and / or 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.55 μm or less, 0.5 μm or less, 0.45 μm or less, or 0.42 μm or less, or 0.1 to 0.8 μm, 0.15 to 0.7 μm, 0.2 to 0.55 μm, or 0.22 to 0.45 μm. [4] A curable resin composition according to any one of [1] to [3], wherein the arithmetic mean surface roughness Ra (μm) in the B-stage state is 0.005 μm or more, 0.01 μm or more, 0.015 μm or more, 0.02 μm or more, or 0.025 μm or more, and / or 0.2 μm or less, 0.15 μm or less, 0.1 μm or less, 0.08 μm or less, 0.07 μm or less, or 0.06 μm or less, or 0.005 to 0.2 μm, 0.01 to 0.15 μm, 0.015 to 0.1 μm, or 0.025 to 0.06 μm.[5] A curable resin composition according to any one of [1] to [4], wherein the G / R value in formula (1) is 170 or more, 180 or more, 190 or more, or 200 or more, and / or 800 or less, 700 or less, 600 or less, or 500 or less, or 160 to 800, 170 to 700, 180 to 600, 190 to 600, or 200 to 500. [6] A curable resin composition according to any one of [1] to [5], wherein the thermosetting resin (A) comprises at least one selected from the group consisting of epoxy resin, maleimide resin, polyimide compound, polyphenylene ether resin, siloxane compound, and (meth)acrylate compound. [7] A curable resin composition according to [6], wherein the epoxy resin comprises at least one selected from the group consisting of aminophenol-type epoxy resin, bisphenol-type epoxy resin, and trisphenolmethane-type epoxy resin. [8] A curable resin composition according to any one of [1] to [7], which contains or does not contain a compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure. [9] A curable resin composition according to any one of [1] to [8], wherein the content of thermosetting resin (A) is 3% by mass or more, 6% by mass or more, 8% by mass or more, or 10% by mass or more, and / or 50% by mass or less, 40% by mass or less, 30% by mass or less, or 25% by mass or less, or 3 to 50% by mass, 6 to 40% by mass, 8 to 30% by mass, or 10 to 25% by mass.

[10] A curable resin composition according to any one of [1] to [9], wherein the content of thermosetting resin (A) relative to nonvolatile matter (100% by mass) is 3% by mass or more, 6% by mass or more, 8% by mass or more, 10% by mass or more, or 12% by mass or more, and / or 60% by mass or less, 50% by mass or less, 40% by mass or less, 36% by mass or less, or 32% by mass or less, or 3 to 60% by mass, 6 to 50% by mass, 8 to 40% by mass, 10 to 36% by mass, or 12 to 32% by mass.

[11] A curable resin composition according to any one of [6] to

[10] , wherein the content of epoxy resin relative to thermosetting resin (A) (100% by mass) is 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.

[12] A curable resin composition according to any one of [8] to

[11] , wherein the content of a compound having a radically polymerizable unsaturated group and a polyalkylene oxide structure relative to the thermosetting resin (A) (100% by mass) is 32% by mass or less, 16% by mass or less, 8% by mass or less, 2% by mass or less, or 1% by mass or less, or substantially none.

[13] A curable resin composition according to any one of [6] to

[12] , wherein the content of a solid epoxy resin relative to the epoxy resin (100% by mass) is 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more, and / or 90% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less.

[14] A curable resin composition according to any one of [1] to

[13] , further comprising at least one selected from the group consisting of a curing agent (B1) and a curing accelerator (B2).

[15] The curable resin composition according to

[14] , comprising at least one selected from the group consisting of amine-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, active ester-based curing agents, and dicyandiamide as the curing agent (B1).

[16] The curable resin composition according to

[14] or

[15] , comprising or not comprising a catechol resorcinol novolac resin as the curing agent (B1).

[17] The curable resin composition according to any one of

[14] to

[16] , wherein the content of the curing agent (B1) is 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, and / or 20% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less, or 0.05 to 20% by mass, 0.1 to 10% by mass, 0.2 to 5% by mass, 0.3 to 3% by mass, or 0.3 to 2% by mass.

[18] A curable resin composition according to any one of

[14] to

[17] , wherein the content of the curing agent (B1) relative to the nonvolatile content (100% by mass) is 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, and / or 20% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less, or 0.05 to 20% by mass, 0.1 to 10% by mass, 0.2 to 5% by mass, 0.3 to 3% by mass, or 0.3 to 2% by mass.

[19] A curable resin composition according to any one of

[14] to

[18] , wherein the content of the curing agent (B1) relative to the thermosetting resin (A) (100% by mass) is 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, or 2% by mass or more, and / or 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 8% by mass or less, 6% by mass or less, or 5% by mass or less, or 0.1 to 20% by mass, 0.5 to 15% by mass, 1 to 10% by mass, 2 to 8% by mass, or 2 to 5% by mass.

[20] A curable resin composition according to any one of

[14] to

[19] , wherein the curing accelerator (B2) comprises at least one selected from the group consisting of an imidazole-based curing accelerator, a tertiary amine-based curing accelerator, and a phosphorus-based curing accelerator.

[21] A curable resin composition according to any one of

[14] to

[20] , wherein the content of the curing accelerator (B2) is 0.01% by mass or more, 0.02% by mass or more, 0.04% by mass or more, or 0.06% by mass or more, and / or 3% by mass or less, 1% by mass or less, 0.6% by mass or less, or 0.3% by mass or less, or 0.01 to 3% by mass, 0.02 to 1% by mass, 0.04 to 0.6% by mass, or 0.06 to 0.3% by mass.

[22] A curable resin composition according to any one of

[14] to

[21] , wherein the content of the curing accelerator (B2) relative to the nonvolatile content (100% by mass) is 0.01% by mass or more, 0.02% by mass or more, 0.04% by mass or more, or 0.06% by mass or more, and / or 3% by mass or less, 1% by mass or less, 0.6% by mass or less, or 0.3% by mass or less, or 0.01 to 3% by mass, 0.02 to 1% by mass, 0.04 to 0.6% by mass, or 0.06 to 0.3% by mass.

[23] A curable resin composition according to any one of

[14] to

[22] , wherein the content of the curing accelerator (B2) relative to the thermosetting resin (A) (100% by mass) is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, and / or 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less, or 0.01 to 4% by mass, 0.05 to 3% by mass, 0.1 to 2% by mass, or 0.2 to 1% by mass.

[24] A curable resin composition according to any one of [1] to

[23] , comprising at least one selected from the group consisting of silica (silicon dioxide), silicon carbide, silicon nitride, alumina (aluminum oxide), aluminum nitride, aluminum hydroxide, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, barium sulfate, barium carbonate, titanium oxide, lime sulfate, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and surface-treated products thereof as an inorganic filler (C).

[25] A curable resin composition according to any one of [1] to

[24] , comprising at least one selected from the group consisting of an inorganic filler (C1) whose surface is not treated and an inorganic filler (C2) whose surface is modified with a silane coupling agent as an inorganic filler (C2).

[26] The curable resin composition according to

[25] , wherein the silane coupling agent in the inorganic filler (C2) is a silane coupling agent having a (meth)acryloyl group or an amino group (particularly a phenylamino group).

[27] A curable resin composition according to any one of [1] to

[26] , wherein the content of inorganic filler (C) is 30% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, and / or 84% by mass or less, 80% by mass or less, 76% by mass or less, or 72% by mass or less, or 30 to 84% by mass, 40 to 80% by mass, 45 to 76% by mass, or 50 to 72% by mass.

[28] A curable resin composition according to any one of [1] to

[27] , wherein the content of inorganic filler (C) relative to nonvolatile matter (100% by mass) is 40% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, or 65% by mass or more, and / or 92% by mass or less, 90% by mass or less, 88% by mass or less, or 86% by mass or less, or 40 to 92% by mass, 50 to 90% by mass, 55 to 88% by mass, 60 to 86% by mass, or 65 to 86% by mass.

[29] A curable resin composition according to any one of [1] to

[28] , wherein the content of inorganic filler (C) relative to thermosetting resin (A) (100% by mass) is 150% by mass or more, 180% by mass or more, 200% by mass or more, 210% by mass or more, or 220% by mass or more, and / or 1000% by mass or less, 800% by mass or less, 750% by mass or less, 700% by mass or less, or 650% by mass or less, or 150 to 1000% by mass, 180 to 800% by mass, 200 to 750% by mass, 210 to 700% by mass, or 220 to 650% by mass.

[30] A curable resin composition according to any one of

[25] to

[29] , wherein the content of inorganic filler (C1) relative to inorganic filler (C) (100% by mass) is 5% by mass or more, 10% by mass or more, 30% by mass or more, 50% by mass or more, or 80% by mass or more, and / or 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less, or 5 to 90% by mass, 10 to 80% by mass, 30 to 70% by mass, or 50 to 60% by mass.

[31] A curable resin composition according to any one of

[25] to

[30] , wherein the content of inorganic filler (C2) relative to inorganic filler (C) (100% by mass) is 5% by mass or more, 10% by mass or more, 30% by mass or more, or 50% by mass or more, and / or 90% by mass or less, 50% by mass or less, 30% by mass or less, 10% by mass or less, or 1% by mass or less, or 5 to 90% by mass, 5 to 50% by mass, 5 to 30% by mass, or 5 to 10% by mass.

[32] A curable resin composition according to any one of [1] to

[31] , comprising a silane coupling agent (D) having a vinyl group, epoxy group, styryl group, (meth)acryloyl group, amino group (e.g., phenylamino group), isocyanurate group, ureido group, mercapto group, sulfide group, or isocyanate group.

[33] The curable resin composition according to any one of [1] to

[32] , wherein the silane coupling agent (D) is at least one selected from the group consisting of: silane coupling agents having epoxy groups such as 3-glycidyloxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; silane coupling agents having (meth)acryloyl groups such as 3-methacryloxypropyltrimethoxysilane and 8-methacryloxyoctyltrimethoxysilane; silane coupling agents having amino groups (especially phenylamino groups) such as N-phenyl-3-aminopropyltrimethoxysilane and 8-phenylaminooctyltrimethoxysilane; and silane coupling agents having ureido groups such as 3-ureidopropyltriethoxysilane.

[34] A curable resin composition according to any one of [1] to

[33] , wherein the content of the silane coupling agent (D) is 0.005% by mass or more, 0.01% by mass or more, 0.02% by mass or more, or 0.03% by mass or more, and / or 2% by mass or less, 1.6% by mass or less, 1.2% by mass or less, or 1% by mass or less, or 0.005 to 2% by mass, 0.01 to 1.6% by mass, 0.02 to 1.2% by mass, or 0.03 to 1% by mass.

[35] A curable resin composition according to any one of [1] to

[34] , wherein the content of the silane coupling agent (D) relative to the nonvolatile content (100% by mass) is 0.005% by mass or more, 0.01% by mass or more, 0.02% by mass or more, or 0.03% by mass or more, and / or 2% by mass or less, 1.6% by mass or less, 1.2% by mass or less, or 1% by mass or less, or 0.005 to 2% by mass, 0.01 to 1.6% by mass, 0.02 to 1.2% by mass, or 0.03 to 1% by mass.

[36] A curable resin composition according to any one of [1] to

[35] , wherein the content of the silane coupling agent (D) relative to the thermosetting resin (A) (100% by mass) is 0.03% by mass or more, 0.06% by mass or more, 0.09% by mass or more, 0.12% by mass or more, or 0.15% by mass or more, and / or 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, or 0.03 to 30% by mass, 0.06 to 20% by mass, 0.09 to 15% by mass, 0.12 to 15% by mass, or 0.15 to 10% by mass.

[37] A curable resin composition according to any one of [1] to

[36] , wherein the content of the silane coupling agent (D) relative to the inorganic filler (C) (100% by mass) is 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, 0.04% by mass or more, or 0.05% by mass or more, and / or 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1.5% by mass or less, or 0.01 to 5% by mass, 0.02 to 4% by mass, 0.03 to 3% by mass, 0.04 to 2% by mass, or 0.05 to 1.5% by mass.

[38] A curable resin composition according to any one of [1] to

[37] , which contains or does not contain components other than the thermosetting resin (A), curing agent (B1), curing accelerator (B2), inorganic filler (C), silane coupling agent (D), and solvent (F) described below (other components (E)).

[39] The curable resin composition according to

[38] , wherein the content of other components (E) relative to nonvolatile matter (100% by mass) is 10% by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0.1% by mass or less and / or 0.01% by mass or more, or 0.01 to 10% by mass, 0.01 to 5% by mass, 0.01 to 3% by mass, 0.01 to 1% by mass, or 0.01 to 0.1% by mass.

[40] A curable resin composition according to any one of [1] to

[39] , comprising a solvent (F), wherein the content of solvent (F) is 4% by mass or more, 8% by mass or more, 12% by mass or more, or 15% by mass or more, and / or 30% by mass or less, 25% by mass or less, 20% by mass or less, or 18% by mass or less, or 4 to 30% by mass, 8 to 25% by mass, 12 to 20% by mass, or 15 to 18% by mass.

[41] A curable resin composition according to any one of [1] to

[40] , wherein the viscosity at 1 rpm at 25°C is 30 to 1500 Pa·s, 60 to 1200 Pa·s, or 90 to 900 Pa·s.

[42] A curable resin composition according to any one of [1] to

[41] , wherein the viscosity at 10 rpm at 25°C is 30 to 2000 Pa·s, 60 to 1500 Pa·s, 90 to 1200 Pa·s, or 120 to 1000 Pa·s.

[43] A curable resin composition according to any one of [1] to

[42] , wherein the TI value (thixotropic index, 1 rpm / 10 rpm) at 25°C is 0.5 to 1.5, 0.6 to 1.4, or 0.65 to 1.3.

[44] An adhesive film using the curable resin composition described in any one of [1] to

[43] .

[45] A laminated sheet comprising the adhesive film described in

[44] and a substrate.

[46] The laminated sheet described in

[45] , wherein at least one surface of the substrate is subjected to a non-silicone release treatment, and the adhesive film is laminated on the surface.

[47] The laminated sheet described in

[45] or

[46] , wherein the substrate is a PET film.

[48] The laminated sheet described in any one of

[45] to

[47] , wherein the contact angle with pure water at the surface of the substrate is 70 to 120°.

[49] A laminated sheet according to any one of

[45] to

[48] , wherein the peel strength of the 31B tape on the surface of the substrate is 100 mN / 25 mm or more, 300 mN / 25 mm or more, 500 mN / 25 mm or more, 1000 mN / 25 mm or more, 1500 mN / 25 mm or more, or 2000 mN / 25 mm or more, and / or 4500 mN / 25 mm or less.

[50] A laminated sheet according to any one of

[45] to

[49] used for laminating a semiconductor substrate.

[51] A cured product of the adhesive film according to

[44] .

[52] A semiconductor device comprising the cured product according to

[51] and a semiconductor element and / or a semiconductor substrate.

Claims

1. A curable resin composition comprising a thermosetting resin (A) and an inorganic filler (C), further comprising a silane coupling agent (D), or an inorganic filler (C2) modified with a silane coupling agent as the inorganic filler (C), wherein the curable resin composition satisfies the following formula (1): G / R ≥ 160 (1) (wherein G represents the gloss (%) at an incident angle of 60° in the B-stage state of the curable resin composition. R represents the maximum height roughness Rz (μm) in the B-stage state of the curable resin composition.) 2. The curable resin composition according to claim 1, further comprising at least one selected from the group consisting of a curing agent (B1) and a curing accelerator (B2).

3. The curable resin composition according to claim 1 or 2, wherein the gloss level is 80 to 120%.

4. The curable resin composition according to claim 1 or 2, comprising a silane coupling agent having a phenylamino group as the silane coupling agent (D).

5. The curable resin composition according to claim 1 or 2, comprising alumina or a surface-treated product thereof as an inorganic filler (C).

6. The curable resin composition according to claim 1 or 2, wherein the content of the silane coupling agent (D) relative to the inorganic filler (C) (100% by mass) is 0.03 to 3% by mass.

7. The curable resin composition according to claim 1 or 2, wherein the TI value (1 rpm / 10 rpm) at 25°C is 0.5 to 1.

5.

8. An adhesive film using the curable resin composition according to claim 1 or 2.

9. A laminated sheet comprising the adhesive film and substrate described in claim 8.

10. The laminated sheet according to claim 9, wherein at least one surface of the substrate is subjected to a non-silicone release treatment, and an adhesive film is laminated on the surface.

11. The laminated sheet according to claim 9, wherein the substrate is a PET film.

12. The laminated sheet according to claim 9, wherein the contact angle with pure water at the surface of the substrate is 70 to 120°.

13. The laminated sheet according to claim 9, wherein the peel strength of the 31B tape on the surface of the substrate is 100 mN / 25 mm or more.

14. The laminated sheet according to claim 9, used for laminating a semiconductor substrate.

15. A cured product of the adhesive film according to claim 8.

16. A semiconductor device comprising a cured product according to claim 15 and a semiconductor element and / or a semiconductor substrate.

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