Resin compositions, cured resin compositions, resin films, printed wiring boards, semiconductor wafer packaging, and semiconductor devices.

Abstract

[Problem] To provide a resin composition that yields a cured material with suppressed warpage and excellent long-term reliability; and a cured material of the resin composition, a resin film, a printed wiring board, a semiconductor wafer package, and a semiconductor device. [Solution] A resin composition comprising (A) an epoxy resin and (B) a curing agent, wherein the average linear thermal expansion coefficient α of the cured material divided by the crosslinking density n of the cured material, Zf (ppm･cm3 / mol･K), satisfies 145<Zf<1300.

Description

[Technical Field]

[0001] This invention relates to resin compositions. Furthermore, it relates to cured forms of the resin composition, resin films, printed circuit boards, semiconductor wafer packages, and semiconductor devices. [Previous Technology]

[0002] Printed wiring boards for semiconductor devices typically include an insulating layer. A resin composition is used as the insulating material constituting this insulating layer. Patent Document 1 discloses an insulating material comprising a thermosetting compound and a curing agent (see claim 1). Such resin compositions are also used for packaging semiconductor wafers. [Prior Art Documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-188667 [Summary of the Invention]

[0004] [Problem to be solved by the invention] When packaging semiconductor wafers (especially when packaging one side of a semiconductor wafer), warping sometimes occurs due to stress deviation. Therefore, it is sought to suppress warping.

[0005] Furthermore, some resin compositions contain thermoplastic resins. By including a thermoplastic resin, the elastic modulus of the cured resin composition decreases, which is expected to suppress warpage in semiconductor wafers. However, the inventors' research has found that using a resin composition containing a thermoplastic resin results in decreased long-term reliability. Long-term reliability can be confirmed, for example, by performing an HTS (High Thermal Storage) test on a test piece and comparing the small change in physical properties before and after the test. That is, it has been found that simply adjusting the elastic modulus of the cured resin composition is insufficient to suppress warpage and achieve excellent long-term reliability. Therefore, it is desirable to provide a resin composition that, if adjustments other than the elastic modulus are made, can produce a cured product with suppressed warpage and excellent long-term reliability regardless of the presence or content of a thermoplastic resin.

[0006] The object of the present invention is to provide a resin composition that yields a cured product with suppressed warpage and excellent long-term reliability; and a cured product of the resin composition, a resin film, a printed circuit board, a semiconductor wafer package, and a semiconductor device. [Means for Solving the Problem]

[0007] The inventors, through in-depth research on resin compositions containing (A) epoxy resin and (B) hardener, discovered that by using the average linear thermal expansion coefficient α of the cured resin composition and the crosslinking density n of the cured resin composition as parameters, and by ensuring that the value Zf (ppm･cm3 / mol･K) of the average linear thermal expansion coefficient α divided by the crosslinking density n satisfies 145<Zf<1300, the above-mentioned problem can be solved, and the present invention is thus completed.

[0008] That is, the present invention includes the following. [1] A resin composition comprising (A) an epoxy resin and (B) a curing agent, characterized in that the average linear thermal expansion coefficient α (ppm / K) of the cured product obtained by curing the resin composition at 180°C for 90 minutes is divided by the crosslinking density n (mol / cm3) of the cured product, and the value Zf (ppm･cm3 / mol･K) satisfies the following formula: 145<Zf<1300. [2] The resin composition as described in [1] further comprises (C) an inorganic filler. [3] The resin composition as described in [2] wherein when the non-volatile component in the resin composition is defined as 100% by mass, the content of component (C) is 70% by mass or more. [4] The resin composition as described in [2] or [3] wherein the average particle size of component (C) is 10 μm or less. [5] A resin composition as described in any one of [1] to [4], wherein component (B) comprises a maleimide compound having at least one hydrocarbon chain of an alkyl group having 5 or more carbon atoms and an alkyl group having 5 or more carbon atoms that may have substituents. [6] A resin composition as described in any one of [1] to [5], wherein when the non-volatile component in the resin composition is defined as 100% by mass, the content of component (B) is 0.5% by mass or more. [7] A resin composition as described in any one of [1] to [6], further comprising (D) a thermoplastic resin. [8] A resin composition as described in [7], wherein when the non-volatile component in the resin composition is defined as 100% by mass, the content of component (D) is 25% by mass or less. [9] The resin composition described in any one of [1] to [8], wherein the glass transition temperature Tg of the aforementioned cured material is in the range of 150 to 240 °C.

[10] The resin composition described in any one of [1] to [9], wherein the average linear thermal expansion coefficient α of the aforementioned cured material is 25 ppm / K or less.

[11] The resin composition described in any one of [1] to

[10] , wherein the storage modulus E' of the aforementioned cured material at a specified temperature T (K) does not reach 1.50 × 10⁹ Pa, where the specified temperature T (K) is the sum of the glass transition temperature Tg (°C) and 353 (K) of the cured material.

[12] The resin composition described in any one of [1] to

[11] , wherein the crosslinking density n of the aforementioned cured material is 0.15 mol / cm³ or less.

[13] The resin composition described in any of [1] to

[12] , wherein the aforementioned value Zf satisfies the following formula: 150 ≦ Zf < ≦ 1000.

[14] The resin composition described in any of [1] to

[13] is used for forming an insulating layer.

[15] The resin composition described in any of [1] to

[14] is used for forming a solder resist layer.

[16] A cured resin composition as described in any one of [1] to

[15] .

[17] A resin sheet comprising a support and a resin composition layer disposed on the support, the resin composition layer comprising a resin composition as described in any one of [1] to

[15] .

[18] A printed wiring board comprising an insulating layer formed by a cured resin composition as described in any one of [1] to

[15] or a cured resin composition as described in

[16] .

[19] A semiconductor wafer package comprising a printed wiring board as described in

[18] and a semiconductor wafer mounted on the printed wiring board.

[20] A semiconductor wafer package comprising a semiconductor wafer and a cured resin composition as described in any one of [1] to

[15] or a cured resin composition as described in

[16] encapsulating the semiconductor wafer.

[21] A semiconductor device comprising a printed wiring board as described in

[18] , or a semiconductor wafer package as described in

[19] or

[20] . [Effects of the invention].

[0009] According to the present invention, a resin composition that can produce a cured material with suppressed warpage and excellent long-term reliability can be provided; as well as a cured material of the resin composition, a resin sheet, a printed wiring board, a semiconductor wafer package, and a semiconductor device.

Implementation Method

[0010] Hereinafter, the resin composition of the present invention, the cured form of the resin composition, the resin film, the printed wiring board, the semiconductor wafer package, and the semiconductor device will be described in detail.

[0011] [Resin Composition] The resin composition of the present invention comprises (A) an epoxy resin and (B) a curing agent. The average linear thermal expansion coefficient α of the cured product obtained by curing the resin composition at 180°C for 90 minutes, divided by the crosslinking density n of the cured product, is Zf (ppm·cm3 / mol·K), which is within the range described below. Based on this resin composition, a cured product with suppressed warpage and excellent long-term reliability can be obtained. Using such a resin composition, cured products of the resin composition, resin films, printed circuit boards, semiconductor wafer packages, and semiconductor devices can be provided.

[0012] The resin composition of the present invention, incorporated into components (A) and (B), may further include any other components. Examples of such other components include (C) inorganic filler, (D) thermoplastic resin, (E) curing accelerator, and (F) other additives (except for components (A) to (E)). Hereinafter, each component contained in the resin composition will be described in detail. Furthermore, in the present invention, the content of each component in the resin composition, unless otherwise specified, is the value when the non-volatile components in the resin composition are defined as 100% by mass.

[0013] <(A) Epoxy Resin> The resin composition contains (A) epoxy resin. Epoxy resin refers to a resin having one or more epoxy groups in its molecule. By containing (A) epoxy resin in the resin composition, a cured product with a cross-linked structure can be obtained.

[0014] Examples of epoxy resins include bisphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol phenolic varnish type epoxy resin, phenolic phenolic varnish type epoxy resin, tributyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, propyltrimethoxide type epoxy resin, propyltrimethoxide ester type epoxy resin, cresol phenolic varnish type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanediethanol type epoxy resin, naphthyl ether type epoxy resin, trihydroxymethyl type epoxy resin, tetraphenylethane type epoxy resin, etc. Epoxy resins can be used alone or in combination of two or more.

[0015] Epoxy resins containing two or more epoxy groups in the molecule are preferred. When the non-volatile component of the epoxy resin is defined as 100% by mass, epoxy resins containing two or more epoxy groups in the molecule are preferred.

[0016] The epoxy resin may be (A-1) liquid epoxy resin or (A-2) solid epoxy resin. The resin composition may also include (A-1) liquid epoxy resin and (A-2) solid epoxy resin.

[0017] ((A-1) Liquid Epoxy Resin) The term (A-1) liquid epoxy resin refers to an epoxy resin that is liquid at 20°C. It is preferable that the resin composition includes (A-1) liquid epoxy resin. Although liquid epoxy resin is one of the components that tends to lower the glass transition temperature of the cured resin composition, according to the present invention, even if the resin composition contains this component, a cured product with a very low average coefficient of linear thermal expansion and excellent heat resistance can still be obtained.

[0018] As a liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in its molecule is preferred, and an aromatic liquid epoxy resin having two or more epoxy groups in its molecule is even more preferred. In this invention, the term "aromatic epoxy resin" refers to an epoxy resin having an aromatic ring in its molecule.

[0019] As a liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, epoxy propylene ester type epoxy resin, epoxy propylene amine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, epoxy propylene amine type epoxy resin, and epoxy resin with butadiene structure are preferred, with bisphenol A type epoxy resin being more preferred.

[0020] Specific examples of liquid epoxy resins include DIC's "HP4032", "HP4032D", and "HP-4032-SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "jER828EL", "825", and "828EL" (bisphenol A type epoxy resin); and Mitsubishi Chemical's "YX7400" (flexible epoxy resin). Mitsubishi Chemical Corporation's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenolic varnish type epoxy resin); Mitsubishi Chemical Corporation's "630" and "630LSD" (epoxypropylamine type epoxy resin); Nippon Steel & Sumitomo Metal Chemicals' "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX's "EX-721" (epoxypropyl ester type epoxy resin); DAICL's "CELLOXIDE 2021P" (alicyclic epoxy resin with an ester backbone); DAICL's "PB-3600" (epoxy resin with a butadiene structure); and Nippon Steel & Sumitomo Chemical's "ZX1658" and "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane type epoxy resin), etc. These can be used individually or in combination of two or more.

[0021] The content of component (A-1) in the resin composition, from the viewpoint of obtaining the effects caused by the inclusion of component (A-1) (e.g., improved workability and compatibility of resin coatings), is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass or more when the non-volatile component in the resin composition is set at 100% by mass. Although there is no particular limitation on the upper limit of the content of component (A-1) as long as it does not excessively impair the effect of the present invention, it can be set at 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less.

[0022] ((A-2) Solid epoxy resin) Solid epoxy resin refers to epoxy resin that is solid at a temperature of 20°C. While the resin composition, as component (A), may contain only solid epoxy resin (A-2), it is preferable to combine it with liquid epoxy resin (A-1) to include solid epoxy resin (A-2) from the perspectives of reducing the average coefficient of linear thermal expansion and increasing the crosslinking density. As a solid epoxy resin, a solid epoxy resin having three or more epoxy groups in its molecule is preferred.

[0023] As a solid epoxy resin, bisphenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol phenolic varnish type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, with naphthol type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin being even more preferred.

[0024] Examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin); DIC's "N-690" (cresol phenolic varnish type epoxy resin); DIC's "N-695" (cresol phenolic varnish type epoxy resin); and DIC's "HP-7200L", "HP-7200", "HP-7200HH", and "HP-7200" (cresol phenolic varnish type epoxy resin). 0H (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthyl ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (pyrogallol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol phenolic varnish type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.; "ESN485" (naphthol phenolic varnish type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (diphenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. 8800 (anthracene-type epoxy resin); PG-100 and CG-500 manufactured by Osaka Gas Chemical Co., Ltd.; 157S70 (bisphenol A phenolic varnish type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; YL7760 (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; YL7800 (alumina-type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; jER1010 (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; jER1031S (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., etc. These can be used individually or in combination of two or more.

[0025] The content of component (A-2) in the resin composition, from the viewpoint of obtaining the effects caused by the inclusion of component (A-2) (e.g., a reduction in the average coefficient of linear thermal expansion, an improvement in heat resistance, or a good crosslinking density), is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, when the non-volatile component in the resin composition is set to 100% by mass. Although there is no particular limitation on the upper limit of the content of component (A-2) as long as it does not excessively impair the effect of the present invention, from the viewpoint of moderately suppressing the crosslinking density, it can be set to 10% by mass or less, 8% by mass or less, 5% by mass or less, or 3% by mass or less.

[0026] When (A-1) liquid epoxy resin and (A-2) solid epoxy resin are used as component (A), the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.01 to 1:20. By making the mass ratio of (A-1) liquid epoxy resin to (A-2) solid epoxy resin within this range, the following effects can be obtained: i) moderate adhesion when used in the form of resin sheets; ii) sufficient flexibility and improved workability when used in the form of resin sheets; and iii) a hardened material with sufficient breaking strength. From the perspective of achieving the effects described above (i) to (iii) and from the perspective of moderately suppressing crosslinking density, the mass ratio of (A-1) liquid epoxy resin to (A-2) solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.01 to 1:10, and even better in the range of 1:0.01 to 1:8.

[0027] From the viewpoint of achieving the desired effect of the present invention, the content of component (A) in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more, when the non-volatile component in the resin composition is defined as 100% by mass. While the upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention is achieved, it can be set to 70% by mass or less, 60% by mass or less, 50% by mass or less, or 35% by mass or less.

[0028] (A) The epoxy equivalent of the component is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 70 g / eq. to 2000 g / eq., and even more preferably 70 g / eq. to 1000 g / eq. By achieving this range, a cured product with sufficient crosslinking density and excellent strength and heat resistance can be produced. Furthermore, the epoxy equivalent can be determined according to JIS K7236, which is the mass of the resin containing 1 equivalent of epoxy groups.

[0029] (A) The weight average molecular weight of the component is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight converted from that of polystyrene by gel permeation chromatography (GPC).

[0030] <(B) Hardener> The resin composition contains a hardener (B). As component (B), a component that can harden component (A) can be used. By containing both epoxy resin (A) and hardener (B) in the resin composition, a hardened product with excellent heat resistance can be obtained.

[0031] Examples of (B) curing agents include (B-1) maleimide-based curing agents and (B-2) curing agents other than maleimide-based curing agents. Examples of curing agents other than (B-2) maleimide-based curing agents include one or more curing agents selected from active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, carbodiimide-based curing agents, benzo[a]pyrene-based curing agents, acid anhydride-based curing agents, amine-based curing agents, and cyanate ester-based curing agents (excluding curing agents containing maleimide groups). A single curing agent may be used alone, or two or more may be used in combination.

[0032] From the viewpoint of achieving the desired effect of the present invention, it is preferable that component (B) contains (B-1) a maleimide-based curing agent. Furthermore, it is preferable that component (B) contains (B-1) a maleimide-based curing agent and (B-2) one or more curing agents selected from those other than maleimide-based curing agents. More preferably, component (B) contains (B-1) a maleimide-based curing agent and (B-2) one or more curing agents selected from those of reactive ester-based curing agents and phenol-based curing agents.

[0033] ((B-1) Maleimide-based curing agent) As a maleimide-based curing agent, example (B-1a) is a maleimide compound having at least one hydrocarbon chain of an alkyl group having 5 or more carbon atoms and a alkyl group having 5 or more carbon atoms, which may have substituents. Also, as a maleimide-based curing agent, example (B-1b) is a maleimide-based curing agent other than component (B-1a). Maleimide-based curing agents can be used alone or in combination of two or more. It is preferable for the maleimide-based curing agent to include component (B-1a), and it is also possible to combine it with a component (B-1b).

[0034] (B-1) The component is a compound containing at least one maleimine group as shown in the following formula in the molecule, preferably a maleimine compound containing an aliphatic structure. In the structure shown in the following formula, the one of the three bonds of the nitrogen atom that is not bonded to other atoms refers to a single bond.

[0035]

[0036] (B-1) The number of maleimine groups in each molecule of the component is more than 1. From the viewpoint of improving the desired effect of the present invention, it is preferable to have more than 2, more preferably more than 3. Although the upper limit is not limited, it can be set to less than 10, less than 6, less than 4, or less than 3.

[0037] The alkyl group containing 5 or more carbon atoms in the maleimine compound with an aliphatic structure preferably has 6 or more carbon atoms, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This alkyl group can be linear, branched, or cyclic, with linear being preferred. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group having 5 or more carbon atoms can be a substituent of an alkenyl group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms can be part of an alkenyl group or part of a polyalkenyl group (preferably with 2 double bonds).

[0038] The carbon number of the alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. This alkyl group can be linear, branched, or cyclic, with linear being preferred. Here, the term "cyclic alkyl group" includes both cases consisting solely of cyclic alkyl groups and cases involving both linear and cyclic alkyl groups. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, heptadecanyl, trihexyhexayl, octyl-cyclohexyl-octyl, propyl-cyclohexyl-octyl, etc. Alkyl groups having 5 or more carbon atoms may be part of an alkenyl group or an alkapolyenylene group (preferably with 2 double bonds).

[0039] From the viewpoint of enhancing the desired effect of the present invention, a maleimide compound containing an aliphatic structure is (B-1a) a maleimide compound having at least one of a hydrocarbon chain having an alkyl group having 5 or more carbon atoms and an alkyl group having 5 or more carbon atoms, wherein a maleimide compound having both an alkyl group having 5 or more carbon atoms and an alkyl group having 5 or more carbon atoms is preferred.

[0040] Alkyl groups having 5 or more carbon atoms and alkyl groups having 5 or more carbon atoms may be in the form of chains, but at least some of their carbon atoms may be bonded together to form rings, and the ring structure may include spirocyclic or condensed rings. Examples of rings formed by mutual bonding include cyclohexane rings.

[0041] Alkyl groups having 5 or more carbon atoms and alkyl groups having 5 or more carbon atoms may or may not have substituents. Examples of substituents include halogen atoms, -OH, -O-C1-10 alkyl, -N(C1-10 alkyl)2, C1-10 alkyl, C6-10 aryl, -NH2, -CN, -C(O)O-C1-10 alkyl, -COOH, -C(O)H, -NO2, etc. Here, the term "Cx-y" (where x and y are positive integers satisfying x < y) indicates that the number of carbon atoms of the organogroup immediately following this term is x to y. For example, the expression "C1-10 alkyl" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may bond together to form a ring, and the ring structure may include spirocyclic or condensed rings. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of alkyl groups having 5 or more carbon atoms and alkyl groups having 5 or more carbon atoms. The above-mentioned substituent may further have substituents (hereinafter sometimes referred to as "secondary substituents"). As secondary substituents, unless otherwise specified, the same substituents as those described above may be used.

[0042] In maleimine compounds containing aliphatic structures, it is preferable that the alkyl group having 5 or more carbon atoms and the alkyl group having 5 or more carbon atoms are directly bonded to the nitrogen atom of the maleimine group.

[0043] The number of maleimine groups per molecule of the maleimine compound containing an aliphatic structure may be one, but is preferably two or more, more preferably ten or less, more preferably six or less, and particularly preferably three or less. By having two or more maleimine groups per molecule of the maleimine compound containing an aliphatic structure, the desired effect of the present invention can be improved.

[0044] Maleimine compounds containing an aliphatic structure are preferred, especially those represented by the following general formula (B1). In general formula (B1), M represents a divalent aliphatic hydrocarbon group containing an alkyl group having 5 or more carbon atoms that may have substituents, and L represents a single bond or a divalent linker.

[0045] M represents a divalent aliphatic hydrocarbon group containing an alkyl group having 5 or more carbon atoms that may have substituents. Preferably, M represents an alkyl group, an alkenyl group, or an enpolyalkenyl group having 5 or more carbon atoms that may have substituents (more preferably, the number of double bonds is 2). The alkyl group of M is the same as the alkyl group having 5 or more carbon atoms mentioned above. Examples of substituents for M include halogen atoms, -OH, -O-C1-10 alkyl, -N(C1-10 alkyl)2, C1-10 alkyl, C6-10 aryl, -NH2, -CN, -C(O)O-C1-10 alkyl, -COOH, -C(O)H, -NO2, etc. Here, the term "Cx-y" (where x and y are positive integers satisfying x < y) indicates that the number of carbon atoms of the organogroup immediately following this term is x to y. For example, the designation "C1-10 alkyl" indicates an alkyl group having 1 to 10 carbon atoms. These substituents can bond together to form a ring, and the ring structure may include a spirocyclic or condensed ring. The above-mentioned substituents may further have substituents (hereinafter sometimes referred to as "secondary substituents"). As secondary substituents, the same substituents as those described above may be used, unless otherwise specified. The substituent of M is preferably an alkyl group having 5 or more carbon atoms. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group having 5 or more carbon atoms.

[0046] L represents a single bond or a divalent linkage. Examples of divalent linkages include alkyl, alkenyl, ynyl, aryl, -C(=O)-, -C(=O)-O-, -NR0- (R0 is a hydrogen atom and an alkyl group with 1 to 3 carbon atoms), oxygen atom, sulfur atom, C(=O)NR0-, divalent groups derived from phthalimide, divalent groups derived from pyromellitic acid diimide, and groups formed by combinations of two or more such divalent groups. Alkenyl, alkenyl, ynyl, aryl, divalent groups derived from phthalimide, divalent groups derived from pyromellitic acid diimide, and groups formed by combinations of two or more such divalent groups may also have an alkyl group with 5 or more carbon atoms as a substituent.

[0047] The term "divalent group derived from phthalimide" refers to a divalent group derived from phthalimide, specifically the group shown in the following general formula. In the formula, "*" indicates a bond.

[0048] The divalent group derived from pyromellitic diimide refers to the divalent group derived from pyromellitic diimide, specifically the group shown in the following general formula. In the formula, "*" indicates the bonding site.

[0049] The alkyl group that forms the divalent linker in L is preferably an alkyl group with 1 to 50 carbon atoms, more preferably an alkyl group with 1 to 45 carbon atoms, and especially preferably an alkyl group with 1 to 40 carbon atoms. This alkyl group can be linear, branched, or cyclic. Examples of such alkyl groups include methyl ethyl, cyclohexyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, heptadecanyl, trihexyhexayl, octyl-cyclohexyl, octyl-cyclohexyl-octyl, propyl-cyclohexyl-octyl, etc.

[0050] The alkenyl group, which is the divalent linker in L, is preferably an alkenyl group with 2 to 20 carbon atoms, more preferably an alkenyl group with 2 to 15 carbon atoms, and particularly preferably an alkenyl group with 2 to 10 carbon atoms. This alkenyl group can be linear, branched, or cyclic. Examples of such alkenyl groups include methylalkenyl, cyclohexenyl, pentenyl, hexenyl, heptenyl, and octenyl.

[0051] The alynyl group, which is the divalent linker in L, is preferably an alynyl group with 2 to 20 carbon atoms, more preferably an alynyl group with 2 to 15 carbon atoms, and especially preferably an alynyl group with 2 to 10 carbon atoms. This alynyl group can be linear, branched, or cyclic. Examples of such alynyl groups include methyl alynyl, cycloalynyl, alynylpentynyl, alynylhexynyl, alynylheptynyl, alynyloctyynyl, etc.

[0052] Among the divalent linking groups in L, aryl groups with 6 to 24 carbon atoms are preferred, aryl groups with 6 to 18 carbon atoms are even more preferred, aryl groups with 6 to 14 carbon atoms are further preferred, and aryl groups with 6 to 10 carbon atoms are even more preferred. Examples of aryl groups include phenyl, naphthyl, and anthraceneyl groups.

[0053] The divalent linker in L, including the alkyl, alkenyl, ynyl, and aryl groups, may have substituents. As substituents, they are the same as those in M ​​in the general formula (B1), and preferably alkyl groups having 5 or more carbon atoms.

[0054] Examples of divalent groups formed by combining two or more of the divalent groups in L include: divalent groups formed by combining an alkyl group, a divalent group derived from phthalimide, and an oxygen atom; divalent groups formed by combining a divalent group derived from phthalimide, an oxygen atom, an aryl group, and an alkyl group; divalent groups formed by combining an alkyl group and a divalent group derived from pyromellitic acid diimide; etc. A group formed by combining two or more divalent groups can also form a condensation ring or other ring by combining the individual groups. Furthermore, the number of repeating units in a group formed by combining two or more divalent groups can be 1 to 10.

[0055] Wherein, as L in the general formula (B1), it is preferably an aryl group with 6 to 24 carbon atoms that may have substituents, an alkyl group with 1 to 50 carbon atoms that may have substituents, an alkyl group with 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a combination of two or more of these groups. Wherein, as L, it is preferably an alkyl group; a divalent group having the structure of alkyl group-divalent group derived from phthalimide-oxygen atom-divalent group derived from phthalimide; a divalent group having the structure of alkyl group-divalent group derived from phthalimide-oxygen atom-aryl group-alkyl group-aryl group-oxygen atom-divalent group derived from phthalimide; or a divalent group having the structure of alkyl group-divalent group derived from pyromellitic diimide.

[0056] Maleimine compounds containing an aliphatic structure are preferred, especially those represented by the following general formula (B2). In general formula (B2), M1 each independently represents a divalent aliphatic hydrocarbon group containing an alkyl group having 5 or more carbon atoms that may have substituents, and A each independently represents a divalent group containing an alkyl group having 5 or more carbon atoms that may have substituents or an aromatic ring that may have substituents. t represents an integer from 1 to 10.

[0057] M1 is independent and represents a divalent aliphatic hydrocarbon group containing an alkyl group having 5 or more carbon atoms that may have substituents. Preferably, M1 is independent and represents an alkyl group, an alkenyl group, or an enpolyalkenyl group having 5 or more carbon atoms that may have substituents (more preferably, the number of double bonds is 2). M1 is more preferably the same as M in the general formula (B1).

[0058] A independently represents a divalent group having an alkyl group having 5 or more carbon atoms that may have substituents, or an aromatic ring that may have substituents. The alkyl group in A can be chain-like, branched, or cyclic, with cyclic alkyl groups having 5 or more carbon atoms that may have substituents being preferred. The number of carbon atoms in the alkyl group is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Examples of such alkyl groups include those having an octyl-cyclohexyl structure, those having an octyl-cyclohexyl-octyl structure, and those having an propyl-cyclohexyl-octyl structure.

[0059] Examples of aromatic rings among the divalent groups having aromatic rings represented by A include benzene rings, naphthalene rings, anthracene rings, phthalimide rings, pyromellitic acid diimide rings, and aromatic heterocycles, with benzene rings, phthalimide rings, and pyromellitic acid diimide rings being preferred. That is, as divalent groups having aromatic rings, divalent groups having benzene rings that may have substituents, divalent groups having phthalimide rings that may have substituents, and divalent groups having pyromellitic acid diimide rings that may have substituents are preferred. Examples of divalent groups having an aromatic ring include groups composed of a divalent group derived from phthalimide and an oxygen atom; groups composed of a divalent group derived from phthalimide, an oxygen atom, an aryl group, and an alkyl group; groups composed of an alkyl group and a divalent group derived from pyromellitic diimide; groups composed of a divalent group derived from pyromellitic diimide; groups composed of a divalent group derived from phthalimide and an alkyl group; etc. The aforementioned aryl and alkyl groups are the same as the aryl and alkyl groups in the divalent linked groups represented by L in general formula (B1).

[0060] A represents a divalent group having an alkyl group and an aromatic ring, which may have substituents. As substituents, they are the same as those represented by the substituents of M in the general formula (B1).

[0061] As a specific example of the basis represented by A, the following basis can be cited. In the formula, "*" indicates the bond.

[0062] The maleimine compound shown in general formula (B2) is preferably either the maleimine compound shown in general formula (B2-1) or the maleimine compound shown in general formula (B2-2). In general formula (B2-1), M2 and M3 each independently represent a divalent aliphatic hydrocarbon group containing an alkyl group having 5 or more carbon atoms that may have substituents, and R30 each independently represents an oxygen atom, an aryl group, an alkyl group, or a divalent group formed by a combination of two or more of these groups. t1 represents an integer from 1 to 10. In general formula (B2-2), M4, M6, and M7 each independently represent a divalent aliphatic hydrocarbon group containing an alkyl group having 5 or more carbon atoms that may have substituents, M5 each independently represents a divalent group having an aromatic ring that may have substituents, and R31 and R32 each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer from 0 to 10, and u1 and u2 each independently represent an integer from 0 to 4.

[0063] M2 and M3 are independent and represent divalent aliphatic hydrocarbon groups containing alkyl groups with 5 or more carbon atoms that may have substituents. Preferably, M2 and M3 are independent and represent alkyl groups, alkenyl groups, or polyalkenyl groups (more preferably, the number of double bonds is 2) with 5 or more carbon atoms that may have substituents. M2 and M3 are more preferably the same as the alkyl groups with 5 or more carbon atoms represented by M in the general formula (B1), with hexadecyl being more preferred.

[0064] R30 is independent and represents an oxygen atom, an aryl group, an alkyl group, or a group formed by a combination of two or more divalent groups. The aryl group and the alkyl group are the same as the aryl group and the alkyl group represented by L in the general formula (B1). As R30, it is preferred to be a group or an oxygen atom formed by a combination of two or more divalent groups.

[0065] Examples of groups in R30 that are composed of two or more divalent groups include combinations of oxygen atoms, aryl groups, and alkyl groups. Specific examples of groups composed of two or more divalent groups include the following groups. In the formula, "*" indicates a bonded area.

[0066] M4, M6, and M7 are each independent and represent a divalent aliphatic hydrocarbon group comprising an alkyl group having 5 or more carbon atoms that may have substituents. Preferably, M4, M6, and M7 are each independent and represent an alkyl group, an alkenyl group, or an polyalkenyl group having 5 or more carbon atoms that may have substituents (more preferably, the number of double bonds is 2). M4, M6, and M7 are the same as the alkyl group having 5 or more carbon atoms that may have substituents represented by M in general formula (B1), with hexyl, heptyl, octyl, nonyl, and decyl being preferred, and octyl being more preferred.

[0067] M5 independently represents a divalent group having an aromatic ring that can have substituents. M5, the same as the divalent group having an aromatic ring that can have substituents represented by A in general formula (B2), is a group formed by a combination of an alkyl group and a divalent group derived from pyromellitic acid diimide; a group formed by a combination of a divalent group derived from phthalimide and an alkyl group is preferred, and a group formed by a combination of an alkyl group and a divalent group derived from pyromellitic acid diimide is even more preferred.

[0068] As a specific example of the base represented by M5, the following base can be cited as an example. In the formula, "*" indicates the bond.

[0069] R31 and R32 each independently represent alkyl groups having 5 or more carbon atoms. R31 and R32 are the same as the alkyl groups having 5 or more carbon atoms mentioned above, with hexyl, heptyl, octyl, nonyl, and decyl being preferred, and hexyl and octyl being even more preferred.

[0070] u1 and u2 each independently represent integers from 1 to 15, with integers from 1 to 10 being preferred.

[0071] Specific examples of maleimine compounds containing an aliphatic structure include compounds (b1), (b2), (b3), (b4), (b5), and (b6) below. However, maleimine compounds containing an aliphatic structure are not limited to these specific examples. In formulas (b1), (b2), (b3), (b5), and (b6), n9, n10, n11, n12, and n13 represent integers from 1 to 10.

[0072] Specific examples of maleimine compounds containing aliphatic structures (component (B-1)) include "BMI-1500" (compound of formula (b1) and compound of formula (b5), "BMI-1700" (compound of formula (b2) and compound of formula (b6), "BMI-3000J" (compound of formula (b3)) and "BMI-689" (compound of formula (b4)) manufactured by Designer Moleculars.

[0073] (B-1) The maleimide equivalent of the component is preferably 50 g / eq. to 2000 g / eq., more preferably 100 g / eq. to 1000 g / eq., and even more preferably 150 g / eq. to 500 g / eq., from the viewpoint of significantly obtaining the desired effect of the present invention. The maleimide equivalent is the mass of a maleimide compound containing 1 equivalent of maleimide.

[0074] Regarding the content of component (B-1), when the non-volatile component of the resin composition is defined as 100% by mass, although it depends on the content of components other than component (A) and component (B-1), from the viewpoint of improving the desired effect of the present invention, it can be defined as 0.2% by mass or more, 0.5% by mass or more, 1.0% by mass or more, or 2.0% by mass or more. From the viewpoint of improving the desired effect of the present invention, the upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less. The proportion of component (B-1) in component (B) is preferably 30% by mass or more, 40% by mass or more, or 50% by mass or more from the viewpoint of improving the desired effect of the present invention, with an upper limit of 100% by mass.

[0075] ((B-2) Curing agents other than maleimine-based curing agents) While there are no particular limitations on the type of active ester-based curing agent, compounds with two or more highly reactive ester groups per molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds, are generally preferred. This active ester-based curing agent is preferably obtained through a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester-based curing agents obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and active ester-based curing agents obtained from carboxylic acid compounds and phenolic compounds and / or naphthol compounds are even better. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, p-phthalic acid, and pyromellitic acid. Examples of phenolic or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, benzotriol, dicyclopentadiene-type diphenol compounds, and phenolic varnishes. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene into two molecules of phenol.

[0076] Specifically, active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated compound of phenolic varnish, and active ester compounds containing a benzoyl compound of phenolic varnish are preferred, among which active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit formed by pentylenyl-dicyclopentyl-pentylphenyl.

[0077] Examples of commercially available active ester-based curing agents include "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "HPC-8000L-65TM" (manufactured by DIC Corporation), which contain a dicyclopentadiene-type diphenol structure; and "EXB-9416-70BK", "EXB-8100L-65T", "EXB-8150-65T", "EXB-8150L-65T", and "H" (manufactured by DIC Corporation), which contain a naphthalene structure. "PC-8150-60T", "HPC-8150-62T", and "HP-B-8151-62T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester compound containing acetylated compounds in phenolic varnishes; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), an active ester curing agent containing acetylated compounds in phenolic varnishes; and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), an active ester curing agent containing acetylated compounds in phenolic varnishes. "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and "PC1300-02-65MA" (manufactured by AIR WATER Corporation), which are active ester compounds containing styrene groups, are examples of such compounds.

[0078] From the viewpoint of heat resistance and water resistance, phenolic curing agents (excluding active ester compounds) and naphthol curing agents (excluding active ester compounds) with a phenolic varnish structure or a cresol-phenolic varnish structure, or naphthol curing agents with a phenolic varnish structure, are preferred. Furthermore, from the viewpoint of adhesion to the conductor layer, nitrogen-containing phenolic curing agents are preferred, and phenolic curing agents with a three-framework structure are even more preferred.

[0079] Specific examples of phenolic curing agents and naphthol curing agents include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Corporation; "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "KA-1160" manufactured by DIC Corporation.

[0080] Specific examples of carbodiimide-based curing agents include "V-03", "V-05", "V-07", "V-09", and "Elastostab H01" manufactured by Nisshinbo Chemical Co., Ltd.

[0081] Specific examples of benzo[a]ene-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Co., Ltd. Benzo[a]ene-based curing agents are compounds having a benzo[a]ene structure. The term "benzo[a]ene structure" refers to a substituted or unsubstituted benzo[a]ene ring (e.g., 1,2-benzo[a]ene ring, 1,3-benzo[a]ene ring), or a benzo[a]ene ring with a portion of its double bonds hydrogenated (e.g., 3,4-dihydro-2H-1,3-benzo[a]ene ring). Examples of anhydride-based curing agents include curing agents having one or more anhydride groups per molecule, with curing agents having two or more anhydride groups per molecule being preferred. Specific examples of anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-di-side-oxytetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic tetracarboxylic anhydride, benzophenone tetracarboxylic dianhydride, and others. Polymer-type acid anhydrides include phenylenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenyltetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-side-oxy-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), and styrene-maleic acid resin copolymerized with styrene and maleic acid. Commercially available anhydride-based curing agents include, for example, "HNA-100," "MH-700," "MTA-15," "DDSA," and "OSA" manufactured by Shin Nippon Rika Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd.; and "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

[0082] As an amine-based curing agent, examples include curing agents having one or more, preferably two or more, amine groups per molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., among which aromatic amines are preferred from the viewpoint of achieving the desired effect of the present invention. Amine-based curing agents are preferably primary or secondary amines, with primary amines being more preferred. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminophen, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylphen, 3,3'-diaminodiphenylphen, m-phenylenediamine, m-carbamoyldiamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino) 4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl) benzoxide, bis(4-(3-aminophenoxy)phenyl) benzoxide, etc. Amine-based hardeners can also be commercially available products, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "EPICURE W" manufactured by Mitsubishi Chemical Co., Ltd.

[0083] Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether, etc., as well as multifunctional cyanate ester resins derived from phenolic varnishes and cresol varnishes, and prepolymers formed by tri-processing a portion of such cyanate ester resins, etc. Specific examples of cyanate ester-based curing agents include Lonza Japan's "PT30" and "PT60" (phenolic varnish-type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resins), "BA230", and "BA230S75" (prepolymers in which part or all of the bisphenol A dicyanate is formed by three-component chemical processes).

[0084] The ratio of (A) epoxy resin to (B) hardener, preferably in the range of 1:0.01 to 1:2, more preferably 1:0.05 to 1:3, and even more preferably 1:0.1 to 1:1.5, is expressed as the ratio of [total number of epoxy groups in the epoxy resin] to [total number of reactive groups in the hardener]. Here, the reactive groups of the hardener (B) are active ester groups, active hydroxyl groups, etc., which vary depending on the type of hardener (B). Furthermore, the total number of epoxy groups in the epoxy resin (A) is the value obtained by dividing the mass of each non-volatile component of the epoxy resin (A) by the epoxy equivalent and summing the values ​​of all epoxy resins. The total number of reactive groups in the hardener (B) is the value obtained by dividing the mass of each non-volatile component of the hardener (B) by the reactive group equivalent and summing the values ​​of all hardeners. By setting the ratio of (A) epoxy resin to (B) hardener within this range, the desired effect of the present invention can be improved.

[0085] The content of component (B) is preferably determined in a manner that satisfies the range of the above-mentioned ratio of epoxy resin (A) to hardener (B). From the viewpoint of enhancing the desired effect of the present invention, the content of component (B) can be set to 0.5% or more, 1% or more, 2% or more, or 3% or more, 50% or less, 40% or less, 30% or less, or 25% or less when the non-volatile matter in the resin composition is defined as 100% by mass.

[0086] <(C) Inorganic filler> The resin composition may also contain (C) inorganic filler. From the viewpoint of reducing the average linear thermal expansion coefficient of the cured resin composition, it is preferable for the resin composition to contain inorganic filler.

[0087] While there are no particular limitations on the materials used for inorganic fillers as long as they are inorganic compounds, examples include silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, gibbsite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium dioxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon dioxide is particularly suitable. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Spherical silicon dioxide is preferred. Inorganic fillers can be used alone or in combination of two or more. Commercially available silicon dioxide fillers include Admatechs' "SO-C2" and "SO-C1", and Denka's "UFP-30" and "UFP-40".

[0088] The average particle size of the inorganic filler is generally 20 μm or less. From the viewpoint of improving the desired effect of the present invention, it is preferably 10 μm or less, more preferably 5.0 μm or less, and even more preferably 2.5 μm or less, and even more preferably 2.0 μm or less. Although there is no particular limitation on the lower limit of the average particle size, it can be set to 1 nm (0.001 μm) or more, or 5 nm or more, or 10 nm or more, etc.

[0089] The average particle size of inorganic fillers can be determined using laser diffraction and scattering based on the Mie scattering theory. Specifically, a laser diffraction and scattering particle size distribution measuring device can be used to create a particle size distribution of the inorganic filler based on volume, and the median diameter can be defined as the average particle size for measurement. Preferably, the sample used for measurement is prepared by dispersing the inorganic filler in methyl ethyl ketone using ultrasound. Laser diffraction and scattering particle size distribution measuring devices such as the "LA-500" manufactured by Horiba Corporation and the "SALD-2200" manufactured by Shimadzu Corporation can be used.

[0090] From the viewpoint of achieving good embeddability, inorganic fillers are preferably treated with a surface treatment agent. Treatment with one or more surface treatment agents containing fluorinated silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, silane coupling agents, alkoxy silane compounds, organosilazane compounds, titanate coupling agents, etc., is even more preferred. Treatment with an amino silane coupling agent is particularly preferred. Other components of the surface treatment agent, such as those having functional groups that react with the resin, such as epoxy, amino, or mercapto groups, are preferred, and it is even more preferable that these functional groups are bonded to the terminal groups. Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd.'s silane-based coupling agents "KBM403" (3-epoxypropoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), and "KBM573" (N-phenyl-3-) silane-based coupling agents. Silane coupling agents such as 3,3,3-trifluoropropyltrimethoxysilane, SZ-31 (hexamethyldisilazane), KBM103 (phenyltrimethoxysilane), KBM-4803 (long-chain epoxy silane coupling agent), and KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane) are manufactured by Shin-Etsu Chemical Co., Ltd.

[0091] From the perspective of achieving good embeddability, the degree of surface treatment by the surface treatment agent is better when the surface is treated with 0.2 to 5 parts by mass of the surface treatment agent, 0.2 to 4 parts by mass, or 0.3 to 3 parts by mass, relative to 100 parts by mass of component (C).

[0092] The degree of surface treatment using the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of good embeddability, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m² or higher, more preferably 0.1 mg / m² or higher, and even better than 0.2 mg / m² or higher. On the other hand, from the viewpoint of suppressing the increase of melt viscosity of the resin coating and melt viscosity in flake form, it is preferably 1 mg / m² or lower, more preferably 0.8 mg / m² or lower, and even better than 0.5 mg / m² or lower.

[0093] The carbon content per unit surface area of ​​the inorganic filler can be determined after the surface-treated inorganic filler has been washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler, and it is ultrasonically washed at 25°C for 5 minutes. After removing the supernatant and drying the non-volatile components, the carbon content per unit surface area of ​​the inorganic filler can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Corporation can be used.

[0094] The specific surface area of ​​component (C) is preferably 1 m² / g or more, more preferably 2 m² / g or more, and especially preferably 3 m² / g or more. While there is no particular upper limit, it is preferably 60 m² / g or less, 50 m² / g or less, or 40 m² / g or less. The specific surface area is calculated using the BET method, employing a fully automated BET specific surface area measuring device (MOUNTECH "Macsorb HM-1210") to adsorb nitrogen onto the sample surface, and using the BET multi-point method.

[0095] (C) The content of component (C) is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and particularly preferably 70% by mass or more or 71% by mass or more, when the non-volatile component in the resin composition is set to 100% by mass. Although there is no particular upper limit, it is usually set to 95% by mass or less, 94% by mass or less, or 93% by mass or less. As illustrated in the embodiments of the present invention, it has been confirmed that when the non-volatile component in the resin composition is set to 100% by mass, even if the content of component (C) is 70% by mass or more, warpage can be suppressed, and a cured product with excellent long-term reliability can be obtained.

[0096] <(D) Thermoplastic Resin> The resin composition may contain (D) thermoplastic resin as an optional component. When the resin composition is processed in the form of resin sheets or films, it is preferable that the resin composition contains the (D) component. However, the resin composition may not contain the (D) component if the value Zf described below is within the defined range.

[0097] (D) The weight-average molecular weight (Mw) of the polystyrene component is preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more, or 3000 or more. The upper limit is preferably 1,000,000 or less, and even more preferably 900,000 or less. (D) The number-average molecular weight (Mn) of the polystyrene component is preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more, or 3000 or more. The upper limit is preferably 1,000,000 or less, and even more preferably 900,000 or less. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polystyrene component are determined by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polystyrene (D) were measured using a Shimadzu LC-9A / RID-6A measuring apparatus, a Showa Denko Shodex K-800P / K-804L / K-804L column, and chloroform as the mobile phase. The column temperature was measured at 40°C, and the values ​​were calculated using a calibration curve of standard polystyrene.

[0098] Examples of (D) thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyamide-imide resins, polyether-imide resins, polyurethane resins, polyether-urethane resins, polyphenylene ether resins, polyether ether ketone resins, and polyester resins, with phenoxy resins being preferred. A single thermoplastic resin may be used alone, or two or more may be used in combination.

[0099] Examples of phenoxy resins include those having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenol acetophenone, phenolic varnish, biphenyl, fenestrated, dicyclopentadiene, norcamphene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane. The terminal group of the phenoxy resin may be a functional group such as a phenolic hydroxyl group or an epoxy group. Phenoxy resins may be used alone or in combination of two or more. Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing a bisphenol A backbone), "YX8100" (a phenoxy resin containing a bisphenol S backbone), and "YX6954" (a phenoxy resin containing a bisphenol acetophenone backbone). Other examples include Nippon Steel Chemical & Materials Co., Ltd.'s "FX280" and "FX293", Mitsubishi Chemical's "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482", etc.

[0100] Examples of polyvinyl acetal resins include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include "Electro-butyral 4000-2", "Electro-butyral 5000-A", "Electro-butyral 6000-C", and "Electro-butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd., and the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd.

[0101] Specific examples of polyimide resins include “RIKACOAT SN20” and “RIKACOAT PN20” manufactured by Shin Nippon Rikan Co., Ltd.

[0102] Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Further examples of polyamide-imide resins include modified polyamides such as "KS9100" and "KS9300" (polysiloxane backbone containing polyamide-imide) manufactured by Hitachi Chemical Industries Co., Ltd.

[0103] Specific examples of polyether ether resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyphenylene ether resins include "OPE-2St 1200" oligophenylene ether / styrene resin manufactured by Mitsubishi Gas Chemical Co., Ltd. Specific examples of polyether ether ketone resins include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE.

[0104] As a specific example of polyurethane resin, examples include polyurethane "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0105] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin elastomers such as polypropylene and ethylene-propylene block copolymer.

[0106] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, etc.

[0107] As component (D), a resin having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkyloxy, polyisoprene, polyisobutylene, and polycarbonate is preferred. A resin having one or two or more structures selected from polybutadiene, poly(meth)acrylate, polyalkyloxy, polyisoprene, polyisobutylene, and polycarbonate is even more preferred. A resin having one or more structures selected from polybutadiene and polycarbonate is further preferred. Furthermore, the term "(meth)acrylate" encompasses methacrylates and acrylates, as well as combinations thereof. These structures may be contained in the main chain or in the side chains.

[0108] Component (D) is preferably composed of a reactive functional group (hereinafter also referred to as "reactive functional group"), thereby becoming able to be incorporated into the cross-linked structure formed by components (A) and (B). Furthermore, the reactive functional group may be one that exhibits reactivity upon heating or light irradiation.

[0109] Examples of reactive groups in component (D) include hydroxyl, carboxyl, amino, vinyl, acrylonitrile, and methacryl. Instead of vinyl, groups with carbon-carbon double bonds can also be used. From the viewpoint of improving the heat resistance of the cross-linked structure, phenolic hydroxyl groups are preferred.

[0110] (D) A suitable embodiment of the component is a resin containing a polybutadiene structure, which may be contained in the main chain or in the side chain. Furthermore, the polybutadiene structure may be partially or completely hydrogenated. The resin containing the polybutadiene structure is called a polybutadiene resin.

[0111] Specific examples of polybutadiene resins include Cray Valley's "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" (containing anhydride groups in polybutadiene), Nippon Soda's "GQ-1000" (hydroxyl and carboxyl-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (two-terminated hydroxyl polybutadiene), "GI-1000", "GI-2000", and "GI-3000" (two-terminated hydrogenated polybutadiene), and Nagase. ChemteX's "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), etc. Furthermore, as the polybutadiene resin, thermoplastic resin A containing reactive functional groups, or a modification thereof, can be used in the thermoplastic resin solution A prepared in the section on "Preparation of Thermoplastic Resin Solution A" described later. Also, as the polybutadiene resin, a resin or a modification thereof containing residues formed by removing the hydroxyl groups from the difunctional hydroxyl groups of polybutadiene, as disclosed in Japanese Patent Application Publication No. 2006-037083, is also preferred. From the viewpoint of obtaining a cured product with excellent flexibility, a resin or a modification thereof containing residues formed by removing the hydroxyl groups from the difunctional hydroxyl groups of polybutadiene with an average molecular weight of 800-1000, or a resin or a modification thereof containing 45% by mass or more of the polybutadiene structure, is preferable. Furthermore, as a polybutadiene resin, resins or modifications thereof having a polybutadiene structure, as disclosed in International Publication No. 2008 / 153208, which use polybutadiene polyol compounds having two or more alcoholic hydroxyl groups per molecule as raw materials, are also acceptable. From the viewpoint of obtaining a cured product with excellent flexibility, resins or modifications thereof having a polybutadiene structure using polybutadiene polyol compounds as raw materials with a number average molecular weight of 300 to 5000 are preferred. The butadiene structure content in the polybutadiene resin is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, 65% by mass or more, or 70% by mass or more. The upper limit of the butadiene structure content is naturally determined by other structural sites in the molecule.

[0112] (D) A suitable embodiment of the component is a resin containing a poly(meth)acrylate structure. A resin containing a poly(meth)acrylate structure is called a poly(meth)acrylate resin. Examples of poly(meth)acrylate resins include Teisan Resin manufactured by Nagase ChemteX, and "ME-2000", "W-116.3", "W-197C", "KG-25", and "KG-3000" manufactured by Negami Kogyo Co., Ltd.

[0113] (D) A suitable embodiment of the component is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin. Examples of polycarbonate resins include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray. Furthermore, as a polycarbonate resin, a thermoplastic resin B containing reactive functional groups or a modification thereof, as described later in the section on "Preparation of Thermoplastic Resin Solution B", may also be used. Furthermore, as a polycarbonate resin, a resin or its modification thereof having residues formed by removing the hydroxyl groups of polycarbonate diol, as disclosed in International Publication No. 2016 / 129541, may also be used. From the viewpoint of obtaining a cured product with excellent flexibility and chemical resistance, a resin or its modification having residues formed by removing the hydroxyl groups of polycarbonate diol with a hydroxyl equivalent of 250 to 1250 is preferred. Also, as a polycarbonate resin, a resin or its modification having residues formed by removing the hydroxyl groups of polycarbonate polyol may also be used. The content of the carbonate structure in the polycarbonate resin is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 75% by mass or more. The upper limit of the carbonate structure content is naturally determined based on other structural sites in the molecule.

[0114] Furthermore, another embodiment of component (D) is a resin containing a siloxane structure. A resin containing a siloxane structure is called a siloxane resin. Examples of siloxane resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Polysiloxane Co., Ltd., and linear polyimides made from amino-terminated polysiloxanes and tetrabasic anhydrides (International Publication No. 2010 / 053185, Japanese Patent Application Publication No. 2002-012667, and Japanese Patent Application Publication No. 2000-319386, etc.).

[0115] Another embodiment of component (D) is a resin containing an alkyl group or an alkyloxy group. A resin containing an alkyl group is called an alkyl resin, and a resin containing an alkyloxy group is called an alkyloxy resin. For the polyalkyloxy group structure, a polyalkyloxy group with 2 to 15 carbon atoms is preferred, a polyalkyloxy group with 3 to 10 carbon atoms is more preferred, and a polyalkyloxy group with 5 to 6 carbon atoms is even more preferred. Specific examples of alkyl resins and alkyloxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Corporation.

[0116] Another embodiment of component (D) is a resin containing an isoprene structure. A resin containing an isoprene structure is called an isoprene resin. Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

[0117] Another embodiment of component (D) is a resin containing an isobutylene structure. A resin containing an isobutylene structure is called an isobutylene resin. Specific examples of isobutylene resins include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by KANEKA.

[0118] The content of component (D) can be set at 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more when the resin component in the resin composition is defined as 100% by mass. The lower limit, from the viewpoint of achieving the desired effect of containing component (D), is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. The upper limit, from the viewpoint of obtaining a cured product with excellent long-term reliability, is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less. The term "resin component" refers to the component remaining after removing (C) inorganic fillers and (F) other additives from the total components contained in the resin composition.

[0119] The content of component (D) can be set at 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more when the non-volatile component in the resin composition is defined as 100% by mass. The lower limit, from the viewpoint of achieving the desired effect of containing component (D), is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit, from the viewpoint of obtaining a cured product with excellent long-term reliability, is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0120] <(E) Curing Accelerator> The resin composition may contain a (E) curing accelerator. Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators, with phosphorus-based, amine-based, imidazole-based, and metal-based curing accelerators being preferred, and amine-based curing accelerators being even more preferred. One curing accelerator may be used alone, or two or more may be used in combination.

[0121] Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0122] As an amine-based hardening accelerator, examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diacrylbicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine and 1,8-diacrylbicyclo(5,4,0)-undecene being preferred.

[0123] Examples of imidazole-based hardening accelerators include 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tris, 2,4 -diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-tris, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tris, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tris, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triisocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxy Imidazole compounds such as methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazole onium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc., and adducts of imidazole compounds with epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

[0124] As an imidazole-based hardening accelerator, commercially available products can also be used, such as the imidazole compound "1B2PZ" manufactured by Shikoku Chemical Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.

[0125] Examples of guanidine-based hardening promoters include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc., with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

[0126] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetoacetone and cobalt(III) acetoacetone, organocopper complexes such as copper(II) acetoacetone, organozinc complexes such as zinc(II) acetoacetone, organoiron complexes such as iron(III) acetoacetone, organonickel complexes such as nickel(II) acetoacetone, and organomanganese complexes such as manganese(II) acetoacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0127] When the resin composition contains component (E), the content of component (E) is typically 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.02% by mass or more, when the non-volatile matter in the resin composition is defined as 100% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. This reliably promotes the curing of the resin composition.

[0128] <(F) Any additives> In one embodiment, the resin composition may, as needed, contain (F) other additives (except for components (A) to (E)). Examples of such other additives include organometallic compounds such as organic fillers, organocopper compounds, organozinc compounds and organocobalt compounds, as well as resin additives such as tackifiers, defoamers, leveling agents, adhesion promoters and colorants.

[0129] As an organic filler, any organic filler that can be used to form the insulating layer of a printed wiring board can be used, such as rubber particles, polyamide microparticles, polysiloxane particles, etc. As rubber particles, commercially available products can also be used, such as "EXL2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3401N" and "AC3816N" manufactured by Aica Industries Co., Ltd.

[0130] (F) The content of the component can be arbitrary as long as it does not excessively impair the desired effect of the present invention. However, when the non-volatile component in the resin composition is set to 100% by mass, for example, it can be 0.1% or more by mass, 0.3% or more by mass, or 0.5% or more by mass. For example, it can be set to 15% or less by mass, 13% or less by mass, or 10% or less by mass.

[0131] <Characteristics of Resin Composition> (Value Zf) Regarding the cured product obtained by curing the resin composition of the present invention at 180°C for 90 minutes, the value Zf (ppm･cm3 / mol･K), obtained by dividing the average linear thermal expansion coefficient α by the crosslinking density n, satisfies 145<Zf<1300, and preferably satisfies 150≦Zf≦1000. Therefore, as exemplified in the Examples section, the resin composition of the present invention, compared with the comparative examples, yields a cured product with suppressed warpage and excellent long-term reliability. Preferably, Zf can be obtained according to the <Obtaining the Value Zf> described later. Zf is typically greater than 145 (ppm·cm3 / mol·K), preferably 150 (ppm·cm3 / mol·K) or more, and from the viewpoint of improving the desired effects of the present invention (warpage suppression and long-term reliability), preferably 155 (ppm·cm3 / mol·K) or more, more preferably 160 (ppm·cm3 / mol·K) or more. It is typically less than 1300 (ppm·cm3 / mol·K), preferably 1000 (ppm·cm3 / mol·K) or less, and from the viewpoint of improving the desired effects of the present invention, preferably 700 (ppm·cm3 / mol·K) or less, more preferably 500 (ppm·cm3 / mol·K) or less. Here, the value Zf can be adjusted, for example, according to the type and amount of components (A) and (B) contained in the resin composition. The value Zf, being a parameter expressed as the relationship between the average linear thermal expansion coefficient α and the crosslinking density n, and being a parameter related to warpage suppression and long-term reliability, can be used as one of the indicators reflecting the presence and content of component (C), which generally reduces the average linear thermal expansion coefficient α; the presence and content of components or parts (e.g., components (C) and (D)) that hinder the formation of crosslinked structures formed by epoxy resin and hardener or can inhibit the increase of crosslinking density; and the presence and content of components (e.g., component (E)) that can promote the formation of the aforementioned crosslinked structures.

[0132] (Glass Transition Temperature Tg) From the viewpoint of obtaining a cured product with excellent heat resistance, the glass transition temperature Tg (°C) of the resin composition of the present invention obtained by curing at 180°C for 90 minutes is preferably in the range of 150~240°C. The glass transition temperature Tg (°C) can be obtained during the <Determination of Dynamic Modulus of Elasticity> described later. The glass transition temperature Tg (°C) is generally 150°C or higher, and from the viewpoint of obtaining a cured product with excellent heat resistance, it is preferably higher than 165°C, and more preferably higher than 176°C. Although the upper limit of the glass transition temperature Tg (°C) is generally 240°C or lower, for example, from the viewpoint of obtaining a cured product with excellent workability, it can be set to 210°C or lower, 209°C or lower, or 205°C or lower.

[0133] (Average linear thermal expansion coefficient α) From the viewpoint of enhancing the desired effect of the present invention, it is preferable that the resin composition of the present invention has a small average linear thermal expansion coefficient α obtained by curing at 180°C for 90 minutes. Here, the value of the average linear thermal expansion coefficient α can be adjusted, for example, to reduce it according to the type and amount of components (A) and (B) contained in the resin composition. The average linear thermal expansion coefficient α can be measured according to the <Determination of Average Linear Thermal Expansion Coefficient (CTE) α> described later. The average linear thermal expansion coefficient α of the cured product is generally less than 30 ppm / K, preferably less than 25 ppm / K, more preferably less than 20 ppm / K. Although the lower limit is not limited, it can be set to more than 1 ppm / K or more than 2 ppm / K for example. From the viewpoint that the above value Zf satisfies the above numerical range, the average linear thermal expansion coefficient α of the cured product can be set to more than 5 ppm / K or more than 7 ppm / K for example.

[0134] (Storage modulus E' at a specified temperature T(K)) Regarding the resin composition of the present invention, for a cured product obtained by curing at 180°C for 90 minutes, the storage modulus E' at a specified temperature T(K) is typically 2.00 × 10⁹ Pa or less. The specified temperature T(K) is the temperature representing the sum of the glass transition temperature Tg(°C) and 353(K) of the cured product (i.e., the value obtained by adding 273K and 80K to the glass transition temperature Tg(°C) to K). Here, the value of the storage modulus E' at the specified temperature T(K) can, for example, be adjusted according to the type and amount of components (A) and (B) contained in the resin composition. From the viewpoint of enhancing the desired effect of the present invention, the storage modulus E' is preferably less than 1.50 × 10⁹ Pa, more preferably less than 1.40 × 10⁹ Pa, even more preferably less than 1.30 × 10⁹ Pa or less than 1.20 × 10⁹ Pa, and typically more than 0.10 × 10⁹ Pa. From the viewpoint of enhancing the desired effect of the present invention, it is preferably more than 0.30 × 10⁹ Pa, more preferably more than 0.35 × 10⁹ Pa, and even more preferably more than 0.40 × 10⁹ Pa. For the hardened material, from the viewpoint that the above value Zf satisfies the above numerical range and enhances the desired effect of the present invention, it is preferable that the average linear thermal expansion coefficient α is less than 25 ppm / K, and the storage modulus E' at the specified temperature T (K) is less than 1.50 × 10⁹ Pa; or, it is preferable that the average linear thermal expansion coefficient α is less than 25 ppm / K, and the storage modulus E' at the specified temperature T (K) is more than 0.30 × 10⁹ Pa. The specified temperature T (K), for example, in the range of 473K to 673K.

[0135] (Crosslinking density n) From the viewpoint of enhancing the desired effect of the present invention, it is preferable that the crosslinking density n of the cured product obtained by curing at 180°C for 90 minutes is 0.15 mol / cm3 or less. Here, the value of the crosslinking density n can be adjusted, for example, according to the type and amount of components such as (A) and (B) contained in the resin composition. The crosslinking density n can be obtained by using the measurement results in the <Determination of Dynamic Elastic Modulus> described later. From the viewpoint of enhancing the desired effect of the present invention, the crosslinking density n is preferably 0.15 mol / cm3 or less, more preferably 0.07 mol / cm3 or less, and even more preferably 0.05 mol / cm3 or less or 0.04 mol / cm3 or less, usually 0.01 mol / cm3 or more, and from the viewpoint of enhancing the desired effect of the present invention, preferably 0.02 mol / cm3 or more, and more preferably 0.03 mol / cm3 or more.

[0136] The resin composition of the present invention can obtain an insulating layer formed by a cured material with suppressed warpage and excellent long-term reliability. Therefore, the resin composition of the present invention is suitable for use as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board), and is more suitable for use as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board). Furthermore, since the resin composition of the present invention produces an insulating layer formed by a cured material with suppressed warpage and excellent long-term reliability, it is also suitable for use in cases where the printed wiring board is a circuit board with components embedded within it. Moreover, since the resin composition of the present invention produces an insulating layer formed by a cured material with suppressed warpage and excellent long-term reliability, it is even more suitable for use as a resin composition for forming a solder resist layer (resin composition for forming a solder resist layer of a printed wiring board). Furthermore, the resin composition of the present invention, since it produces an insulating layer formed by a hardened material with suppressed warpage, is suitable for use as a resin composition for forming an encapsulation layer for semiconductor wafer packaging (resin composition for forming an encapsulation layer for semiconductor wafer packaging). Also, the resin composition of the present invention is suitable for use as a resin composition for forming a rewiring layer for semiconductor wafer packaging (resin composition for forming a rewiring layer for semiconductor wafer packaging).

[0137] A semiconductor wafer package including a redistribution layer is manufactured, for example, by the following steps (1) to (6): (1) applying a temporary fixing film layer to a substrate, (2) temporarily fixing a semiconductor wafer to the temporary fixing film, (3) forming a package layer on the semiconductor wafer, (4) peeling the substrate and the temporary fixing film off the semiconductor wafer, (5) forming a redistribution layer as an insulating layer on the surface of the substrate and the temporary fixing film after peeling off the semiconductor wafer, and (6) forming a redistribution layer as a conductor layer on the redistribution layer. Furthermore, when manufacturing a semiconductor wafer package including a package layer, a redistribution layer may be further formed on the package layer.

[0138] <Method for Manufacturing Resin Composition> The method for manufacturing the resin composition of the present invention is not particularly limited, but examples include methods such as mixing the blended components with solvents or the like and dispersing them using a rotary mixer. When manufacturing the resin composition of the present invention, by selecting component (A) and component (B) and adjusting the content of component (A) and component (B), the aforementioned value Zf can be limited to the aforementioned range.

[0139] The resin composition, for example by including a solvent, can be obtained as a resin coating. Furthermore, from the viewpoint of achieving the desired effect of the present invention, it is preferable to use the resin composition in a stage B state or in a film shape to dry the resin coating.

[0140] <Properties and Uses of Cured Resin Compositions> (Long-Term Reliability) Cured products obtained by thermosetting the resin composition of the present invention generally exhibit excellent long-term reliability. Long-term reliability can be evaluated according to the description in <Evaluation of Long-Term Reliability> below. For example, cured products obtained by thermosetting the resin composition at 180°C for 90 minutes are preferred if the absolute value of the change in tensile breaking strength before and after the HTS test is small (e.g., not reaching 20% ​​or less or 10% or less).

[0141] (Suppression of Warpage) When the cured product obtained by thermosetting the resin composition of the present invention is formed on a substrate, warpage of the substrate is generally suppressed. Warpage can be evaluated according to the description in "Evaluation of Warpage" described later. For example, the maximum amount of warpage that can occur on a substrate on which a cured product with a thickness of 300 μm obtained by thermosetting the resin composition at 180°C for 90 minutes is formed is 2000 μm or less.

[0142] (Chemical Resistance) The cured product obtained by thermosetting the resin composition of the present invention generally exhibits excellent chemical resistance. Chemical resistance can be evaluated according to the description in "Evaluation of Chemical Resistance" described later. For example, a cured product with a thickness of 100 μm obtained by thermosetting the resin composition at 180°C for 90 minutes, even after immersion in a strong alkaline aqueous solution (e.g., potassium hydroxide aqueous solution, tetramethylammonium hydroxide solution, sodium hydroxide aqueous solution, or sodium carbonate aqueous solution), exhibits a mass reduction rate of less than 1% by mass.

[0143] (Glass transition temperature Tg) From the viewpoint of excellent heat resistance, the cured product obtained by thermosetting the resin composition of the present invention has a glass transition temperature Tg (°C) in the range of 150 to 240°C. More preferred ranges are as previously described regarding the resin composition.

[0144] (Average linear thermal expansion coefficient α) From the viewpoint of enhancing the desired effect of the present invention, it is preferable for the cured product obtained by thermosetting the resin composition of the present invention to have a small average linear thermal expansion coefficient α. Further preferred ranges are as previously described regarding the resin composition.

[0145] (Storage modulus E' at a specified temperature T(K)) The cured product obtained by thermosetting the resin composition of the present invention typically has a storage modulus E' of 2.00 × 10⁹ Pa or less at a specified temperature T(K). Preferred ranges, etc., are as previously described with respect to the resin composition.

[0146] (Crosslinking density n) From the viewpoint of enhancing the desired effect of the present invention, the cured product obtained by thermosetting the resin composition of the present invention has a crosslinking density n of 0.15 mol / cm3 or less. Further preferred ranges are as previously described regarding the resin composition.

[0147] (Value Zf) The cured product obtained by thermosetting the resin composition of the present invention preferably has a value Zf (ppm･cm3 / mol･K) obtained by dividing the aforementioned average linear thermal expansion coefficient α by the aforementioned crosslinking density n, which satisfies 145<Zf<1300, and more preferably satisfies 150≦Zf≦1000. Such a cured product, as exemplified in the section on examples, exhibits suppressed warpage and excellent long-term reliability. Further preferred ranges are as previously described regarding the resin composition.

[0148] The cured resin composition of the present invention exhibits suppressed warpage and excellent long-term reliability. Therefore, the cured resin composition of the present invention is suitable for use as an insulating layer of a printed circuit board (PCB) and as an interlayer insulating layer of a PCB. Furthermore, since the cured resin composition of the present invention produces an insulating layer with suppressed warpage and excellent long-term reliability, it is also suitable for use in cases where the PCB is a component-embedded circuit board. Moreover, since the cured resin composition of the present invention produces an insulating layer formed by a cured material with suppressed warpage and excellent long-term reliability, it is even more suitable for use as a solder resist layer. Furthermore, since the cured resin composition of the present invention produces an insulating layer formed by a cured material with suppressed warpage, it is suitable for use as a packaging layer for packaging semiconductor wafers. Furthermore, the cured resin composition of the present invention is suitable for use as a rewiring forming layer (insulating layer) for forming a rewiring layer of a semiconductor wafer package.

[0149] [Resin Sheet] The resin sheet of the present invention comprises a support and a resin composition layer disposed on the support, the resin composition layer comprising the resin composition of the present invention. The resin composition layer may be in a stage B state.

[0150] The thickness of the resin composition layer of the resin sheet is typically 150 μm or less, preferably 110 μm or less. From the perspective of thinning printed circuit boards, it can be set to 50 μm or less or 40 μm or less. This allows for further reduction in thickness. While there is no particular limitation on the lower limit of the resin composition layer thickness, it is generally set to 1 μm or more, 1.5 μm or more, 2 μm or more, etc.

[0151] As a support, examples include films made of plastic materials, metal foils, and release paper, with films and metal foils made of plastic materials being preferred.

[0152] When a film made of plastic material is used as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter referred to as "PET") and polyethylene naphthalate (hereinafter referred to as "PEN"), acrylic-based polyolefins such as polycarbonate (hereinafter referred to as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with low-cost polyethylene terephthalate being particularly good.

[0153] When using metal foil as a support, examples of metal foils include copper foil and aluminum foil, with copper foil being preferred. As copper foil, foil made of copper as a single metal can be used, or foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0154] The support body may be treated with a matte finish, corona treatment, or antistatic treatment on the surface that is bonded to the resin composition layer.

[0155] Furthermore, as a support, it can also be used in a support with a release layer that has a release layer on the surface bonded to the resin composition layer. Examples of release agents used in the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. Commercially available products can also be used as the support for the release layer, such as "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Ltd., "Purex" manufactured by Teijin Corporation, and "Unipeel" manufactured by Unitika Corporation, etc., which are PET films with a release layer and whose main component is an alkyd resin-based release agent.

[0156] While there is no particular limitation on the thickness of the support, a range of 5 μm to 75 μm is preferred, and a range of 10 μm to 60 μm is even more preferred. Furthermore, when using a support with an attached release layer, the overall thickness of the support with the release layer is preferably within the above-mentioned range.

[0157] In one embodiment, the resin sheet may, as needed, contain other layers. Examples of such other layers include, for instance, a protective film based on the support, disposed on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but may be, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of dirt or scratches to the surface of the resin composition layer can be suppressed.

[0158] A resin sheet, for example, can be manufactured by preparing a resin coating made by dissolving a resin composition in an organic solvent, applying the resin coating onto a support using a mold coating machine or the like, and then drying it to form a resin composition layer.

[0159] Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellolytic agents and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and acetamide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. One organic solvent may be used alone, or two or more may be used in combination.

[0160] Drying can be carried out by known methods such as heating or blowing hot air. While there are no particular limitations on the drying conditions, drying is preferably carried out when the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although the drying method varies depending on the boiling point of the organic solvent in the resin coating, for example, when using a resin coating containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0161] The resin sheet can be rolled into a roller for storage. When the resin sheet has a protective film, it becomes usable by peeling off the protective film.

[0162] The resin sheet of the present invention produces an insulating layer formed by a hardened material with suppressed warpage and excellent long-term reliability. Therefore, the resin sheet of the present invention is suitable for use as a resin sheet for forming an insulating layer of a printed wiring board (resin sheet for forming an insulating layer of a printed wiring board), and is more suitable for use as a resin sheet for forming an interlayer insulating layer of a printed wiring board (resin sheet for interlayer insulating layer of a printed wiring board). Furthermore, the resin sheet of the present invention is suitable for use as a resin sheet for forming a solder resist layer of a printed wiring board (resin sheet for forming a solder resist layer of a printed wiring board). Also, since the resin sheet of the present invention produces an insulating layer formed by a hardened material with suppressed warpage, it is suitable for use as a resin composition for forming an encapsulation layer of a semiconductor wafer for semiconductor wafer packaging (resin sheet for forming an encapsulation layer of a semiconductor wafer). Furthermore, the resin sheet of the present invention can be used as a resin sheet for forming a rewiring layer (insulating layer) for semiconductor wafer packaging (resin sheet for forming a rewiring layer for semiconductor wafer packaging).

[0163] <Printed Wiring Board> The printed wiring board of the present invention comprises an insulating layer formed by a cured material containing the resin composition of the present invention. This printed wiring board can be manufactured, for example, by a manufacturing method comprising the following steps (1) and (2): (1) A step of forming a resin composition layer containing the resin composition on a substrate using the resin composition of the present invention. (2) A step of thermally curing the resin composition layer to form an insulating layer.

[0164] In step (1), a substrate is prepared. Examples of substrates include glass epoxy boards, metal substrates (stainless steel or cold-rolled steel sheets (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. Furthermore, the substrate may have a metal layer such as copper foil on its surface, which is part of the substrate. For example, a substrate with a peelable first metal layer and a second metal layer on both surfaces can be used. When using such a substrate, typically, a conductor layer that functions as a wiring layer for circuit wiring is formed on the side of the second metal layer opposite to the first metal layer. Examples of such a substrate with a metal layer include the carrier copper foil with ultra-thin copper foil "Micro Thin" manufactured by Mitsui Mining & Metals Corporation.

[0165] Furthermore, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, the component comprising the substrate and the conductor layer formed on the surface of the substrate will be appropriately referred to as a "substrate with wiring layer". Examples of conductor materials included in the conductor layer include materials selected from one or more metals grouped together with gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Single metals or alloys may be used as conductor materials. Examples of alloys include alloys selected from two or more metals grouped together (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoint of versatility, cost, and ease of patterning in forming the conductor layer, alloys of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals, and nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys as alloys, are preferred. Among them, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper are preferred; as are nickel-chromium alloys; and single metals such as copper are especially preferred.

[0166] The conductor layer, for example, may be patterned to function as a wiring layer. In this case, while there are no particular restrictions on the line width / space ratio of the conductor layer, it is preferably 20 / 20 μm or less (i.e., a spacing of 40 μm or less), more preferably 10 / 10 μm or less, further preferably 5 / 5 μm or less, even more preferably 1 / 1 μm or less, and most preferably 0.5 / 0.5 μm or more. Spacing. It is not necessary for all conductor layers to be the same. The minimum spacing of the conductor layers may, for example, be 40 μm or less, 36 μm or less, or 30 μm or less.

[0167] The thickness of the conductor layer is based on the design of the printed wiring board, but is preferably 3μm to 35μm, more preferably 5μm to 30μm, even more preferably 10μm to 20μm, and especially preferably 15μm to 20μm.

[0168] The conductor layer can be formed, for example, by a method comprising the following steps: laminating a dry film (photosensitive resist film) onto a substrate; exposing and developing the dry film under specified conditions using a photomask to form a patterned dry film; using the developed patterned dry film as a plating mask to form the conductor layer by a plating method such as electroplating; and peeling off the patterned dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, for example, a dry film formed from resins such as phenolic varnish resin and acrylic resin. The lamination conditions between the substrate and the dry film can be the same as those for the lamination conditions between the substrate and the resin sheet described later. The peeling off of the dry film can be carried out, for example, using an alkaline peeling solution such as sodium hydroxide solution.

[0169] After preparing the substrate, a resin composition layer is formed on the substrate. When forming a conductor layer on the surface of the substrate, it is preferable that the resin composition layer is formed by embedding the conductor layer in the resin composition layer.

[0170] The resin composition layer is formed, for example, by laminating a resin sheet to a substrate. This lamination can be performed, for example, by heating and pressing the resin sheet to the substrate from the support side, thereby bonding the resin composition layer to the substrate. Examples of components for heating and pressing the resin sheet to the substrate (hereinafter sometimes referred to as "heat-pressing components") include heated metal plates (such as SUS mirror plates) or metal rollers (such as SUS rollers). Furthermore, instead of directly pressing the resin sheet with the heat-pressing components, it is better to apply pressure using an elastic material such as heat-resistant rubber so that the resin sheet can fully conform to the surface irregularities of the substrate.

[0171] The lamination of the substrate and the resin sheet can be performed, for example, by vacuum lamination. In vacuum lamination, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa. The heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions below 13 hPa.

[0172] After lamination, under normal pressure (atmospheric pressure), for example, the laminated resin sheet can be smoothed by applying pressure from the support side to the heated pressing member. The pressure conditions for the smoothing treatment can be set to the same conditions as the heated pressing conditions for lamination described above. Furthermore, lamination and smoothing treatment can be performed continuously using a vacuum laminator.

[0173] Furthermore, the resin composition layer can be formed, for example, by compression molding. The molding conditions can be the same as those used in the method for forming the resin composition layer in the step of forming the encapsulation layer of a semiconductor wafer package, as described later.

[0174] After forming a resin composition layer on a substrate, the resin composition layer is thermocured to form an insulating layer. The thermocure conditions of the resin composition layer vary depending on the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C), and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

[0175] Before heat curing the resin composition layer, a preheating treatment may be applied to the resin composition layer by heating it at a temperature lower than the curing temperature. For example, before heat curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C or higher but not exceeding 120°C (preferably 60°C or higher but not exceeding 110°C, more preferably 70°C or higher but not exceeding 100°C) for a period of 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

[0176] By performing the above method, a printed wiring board with an insulating layer can be manufactured. Furthermore, the method for manufacturing the printed wiring board may also include any step. For example, when manufacturing the printed wiring board using a resin sheet, the method may include a step of peeling off a support for the resin sheet. The support may be peeled off before or after the thermosetting of the resin composition layer.

[0177] A method for manufacturing a printed wiring board may, for example, include a step of grinding the surface of the insulating layer after the insulating layer has been formed. The grinding method is not particularly limited. For example, a flat grinding disc may be used to grind the surface of the insulating layer.

[0178] A method for manufacturing a printed wiring board may include, for example, a step (3) of interlayer bonding of conductor layers, such as a step of drilling holes in the insulating layer. This allows the formation of vias, through-holes, etc., in the insulating layer. Examples of methods for forming vias include laser irradiation, etching, and mechanical drilling. The size or shape of the via can be appropriately determined according to the output design of the printed wiring board. Furthermore, in step (3), interlayer bonding may be performed by grinding or polishing the insulating layer.

[0179] After the via is formed, it is preferable to perform a step to remove adhesive residue from the via. This step is sometimes called the adhesive residue removal step. For example, when forming a conductor layer on the insulating layer by plating, a wet adhesive residue removal process can be performed on the via. Alternatively, when forming a conductor layer on the insulating layer by sputtering, a dry adhesive residue removal process, such as a plasma treatment process, can be performed. Furthermore, the adhesive residue removal step can roughen the insulating layer.

[0180] Furthermore, before forming a conductor layer on the insulating layer, the insulating layer may be roughened. According to this roughening treatment, typically, the surface of the insulating layer, including the vias, is roughened. As a roughening treatment, either dry or wet roughening treatment can be performed. Examples of dry roughening treatment include plasma treatment. Examples of wet roughening treatment include methods that sequentially perform swelling treatment using a swelling solution, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing solution.

[0181] After forming the via, a conductor layer can be formed on the insulating layer. By forming a conductor layer at the location where the via is formed, the newly formed conductor layer is made connected to the conductor layer on the substrate surface, thus achieving interlayer bonding. Examples of methods for forming the conductor layer include plating, sputtering, and vapor deposition, with plating being preferred. In suitable embodiments, a conductor layer with a desired wiring pattern is formed by plating the surface of the insulating layer using appropriate methods such as semi-additive or fully additive methods. Furthermore, when the support in the resin film is a metal foil, a conductor layer with a desired wiring pattern can be formed using a subtractive process. The material of the formed conductor layer can be a single metal or an alloy. Moreover, this conductor layer can have a single-layer structure or a multi-layer structure containing two or more layers of different types of materials.

[0182] Here, an example of an embodiment in which a conductor layer is formed on an insulating layer is described in detail. A plating seed layer can be formed on the surface of the insulating layer by electroless plating. Next, a masking pattern is formed on the formed plating seed layer, corresponding to a desired wiring pattern, exposing a portion of the plating seed layer. After forming an electroplated layer on the exposed plating seed layer by electroplating, the masking pattern is removed. Then, unwanted plating seed layers can be removed by etching or similar processes to form a conductor layer with the desired wiring pattern. Furthermore, the dry film used to form the masking pattern when forming the conductor layer is the same as the dry film described above.

[0183] The method for manufacturing a printed wiring board may also include a step (4) of removing a substrate. By removing the substrate, a printed wiring board having an insulating layer and a conductor layer embedded therein can be obtained. This step (4) may be performed, for example, when a substrate having a peelable metal layer is reused.

[0184] <Semiconductor Wafer Packaging> A first embodiment of the present invention provides a semiconductor wafer package comprising the aforementioned printed wiring board and a semiconductor wafer mounted on the printed wiring board. This semiconductor wafer package can be manufactured by bonding the semiconductor wafer to the printed wiring board.

[0185] The bonding conditions between the printed circuit board and the semiconductor wafer can be any condition where the terminal electrodes of the semiconductor wafer and the circuit wiring of the printed circuit board are conductively connected. For example, the conditions used in flip chip mounting of semiconductor wafers can be adopted. Also, for example, the semiconductor wafer and the printed circuit board can be bonded through an insulating adhesive.

[0186] As an example of a bonding method, a method of pressing a semiconductor wafer onto a printed wiring board can be cited. As for the pressing conditions, the pressing temperature is typically in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the pressing time is typically in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

[0187] Another example of a bonding method is the method of reflowing a semiconductor wafer onto a printed circuit board. The reflow conditions can be set in the range of 120°C to 300°C.

[0188] After the semiconductor wafer is bonded to the printed wiring board, the semiconductor wafer can be filled with a mold bottom filler. As this mold bottom filler, the above-mentioned resin composition can be used, or the above-mentioned resin sheet can also be used.

[0189] A second embodiment of the semiconductor wafer package of the present invention includes a semiconductor wafer and a cured resin composition encapsulating the semiconductor wafer. In such a semiconductor wafer package, the cured resin composition typically functions as an encapsulation layer. An example of the second embodiment of the semiconductor wafer package is a fan-out type WLP.

[0190] Such a method for manufacturing a semiconductor wafer package may include: (A) a step of applying a temporary fixing film layer to a substrate; (B) a step of temporarily fixing a semiconductor wafer onto the temporary fixing film; (C) a step of forming a packaging layer on the semiconductor wafer; (D) a step of peeling off the substrate and the temporary fixing film from the semiconductor wafer; (E) a step of forming a rewiring layer as an insulating layer on the surface of the substrate and the temporary fixing film after peeling off the semiconductor wafer; (F) a step of forming a rewiring layer as a conductor layer on the rewiring layer; and (G) a step of forming a solder resist layer on the rewiring layer. Furthermore, the aforementioned method for manufacturing a semiconductor wafer package may also include: (H) a step of dicing a plurality of semiconductor wafer packages into individual semiconductor wafer packages for wafer individualization.

[0191] (Step (A)) Step (A) is the step of laminating a temporary fixing film onto a substrate. The lamination conditions between the substrate and the temporary fixing film may be the same as the lamination conditions between the substrate and the resin film in the method for manufacturing a printed wiring board.

[0192] As a substrate, examples include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates in which epoxy resin is infiltrated into glass fibers and then heat-cured; substrates such as BT resins made of bismaleimide triresin; etc.

[0193] The temporary fixing film can be made of any material that can be peeled off from the semiconductor wafer and can temporarily fix the semiconductor wafer. Examples of commercially available products include "REVALPHA" manufactured by Nitto Denko Corporation.

[0194] (Step (B)) Step (B) is the step of temporarily fixing the semiconductor wafer onto the temporary fixing film. The temporary fixing of the semiconductor wafer can be performed, for example, using a flip chip bonder, a die bonder, or other similar device. The layout and number of semiconductor wafers can be appropriately set depending on the shape and size of the temporary fixing film, the production quantity of the target semiconductor wafer package, etc. For example, the semiconductor wafers can be arranged in a matrix of multiple rows and multiple columns for temporary fixing.

[0195] (Step (C)) Step (C) is the step of forming an encapsulation layer on a semiconductor wafer. The encapsulation layer is formed by curing the aforementioned resin composition. The encapsulation layer is typically formed by a method that includes the step of forming a resin composition layer on a semiconductor wafer and the step of thermally curing the resin composition layer to form the encapsulation layer.

[0196] The resin composition layer is preferably formed by compression molding. In compression molding, a semiconductor wafer and a resin composition are typically placed in a mold, and pressure and heat are applied to the resin composition within the mold as needed to form a resin composition layer covering the semiconductor wafer.

[0197] The specific operation of the compression molding method can be performed, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. Furthermore, as mentioned above, a resin composition is coated onto the temporarily fixed semiconductor wafer on the temporary fixing film. The semiconductor wafer coated with the resin composition, along with the substrate and the temporary fixing film, is mounted onto the lower mold. Then, the upper mold and the lower mold are snapped together, and heat and pressure are applied to the resin composition to perform compression molding.

[0198] Furthermore, the specific operation of the compression molding method can be performed, for example, as follows: An upper mold and a lower mold are prepared as molds for compression molding. The resin composition is placed in the lower mold. The semiconductor wafer, substrate, and temporary fixing film are then mounted onto the upper mold. Afterward, the upper and lower molds are fastened together such that the resin composition placed in the lower mold is in contact with the semiconductor wafer mounted on the upper mold, and heat and pressure are applied to perform compression molding.

[0199] Molding conditions vary depending on the composition of the resin composition, and appropriate conditions can be adopted to achieve good encapsulation. For example, the mold temperature during molding is preferably 70°C or higher, more preferably 80°C or higher, particularly preferably 90°C or higher, preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. Furthermore, the pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or higher, more preferably 2 minutes or higher, particularly preferably 3 minutes or higher, preferably 60 minutes or lower, more preferably 30 minutes or lower, and particularly preferably 20 minutes or lower. Generally, the mold is removed after the resin composition layer is formed. Mold removal can be performed before or after the resin composition layer has been heat-cured.

[0200] The resin composition layer can be formed by laminating a resin sheet with a semiconductor wafer. For example, a resin composition layer can be formed on a semiconductor wafer by heating and pressing the resin composition layer of the resin sheet with the semiconductor wafer. The lamination of the resin sheet and the semiconductor wafer can usually be performed in the same way as the lamination of the resin sheet and the substrate in the manufacturing method of a printed circuit board, using a semiconductor wafer instead of a substrate.

[0201] After forming a resin composition layer on a semiconductor wafer, the resin composition layer is thermally hardened to obtain an encapsulation layer covering the semiconductor wafer. This allows for the encapsulation of a semiconductor wafer using the hardened resin composition. The thermal hardening conditions of the resin composition layer can be the same as those used in the printed circuit board manufacturing method. Furthermore, before thermally hardening the resin composition layer, a preheating treatment can be applied to the resin composition layer at a temperature lower than the hardening temperature. The conditions for this preheating treatment can be the same as those used in the preheating treatment in the printed circuit board manufacturing method.

[0202] (Step (D)) Step (D) is the step of peeling the substrate and the temporary fixing film from the semiconductor wafer. The peeling method should preferably be appropriate depending on the material of the temporary fixing film. Examples of peeling methods include heating, foaming, or expanding the temporary fixing film. Alternatively, an example of a peeling method is to reduce the adhesion of the temporary fixing film by irradiating it with ultraviolet light from the substrate.

[0203] In methods of peeling off a temporary fixation film by heating, foaming, or expanding, the heating conditions are typically 100°C to 250°C for 1 to 90 seconds or 5 to 15 minutes. In methods of peeling off a temporary fixation film by irradiating it with ultraviolet light to reduce its adhesiveness, the amount of ultraviolet light irradiated is typically 10 mJ / cm² to 1000 mJ / cm².

[0204] (Step (E)) Step (E) is a step of forming a redistribution layer as an insulating layer on the surface of the substrate and the temporary fixing film of the stripped semiconductor wafer.

[0205] The material for the rewiring layer can be any material with insulating properties. From the viewpoint of ease of manufacturing semiconductor wafer packaging, photosensitive resins and thermosetting resins are preferred. Furthermore, the resin composition of this invention can be used as the thermosetting resin.

[0206] After the rewiring layer is formed, in order to make interlayer connections between the semiconductor wafer and the rewiring layer, vias can be formed in the rewiring layer.

[0207] In the method for forming through-holes when the material of the reconnection forming layer is a photosensitive resin, an active energy line is typically irradiated onto the surface of the reconnection forming layer using a mask pattern, thereby photocuring the irradiated portion of the reconnection forming layer. Examples of active energy lines include ultraviolet light, visible light, electron beams, and X-rays, with ultraviolet light being particularly preferred. The amount and duration of ultraviolet irradiation can be appropriately set depending on the photosensitive resin. Examples of exposure methods include contact exposure, where the mask pattern is in close contact with the reconnection forming layer, and non-contact exposure, where the mask pattern is not in close contact with the reconnection forming layer and parallel light is used for exposure.

[0208] After photocuring the reconnection layer, the reconnection layer is developed to remove unexposed areas and form vias. Development can be performed using either wet or dry development. Examples of development methods include immersion, puddle, spray, brushing, and scraping. From a resolution perspective, puddle development is the most suitable.

[0209] When the material for the rewiring layer is a thermosetting resin, methods for forming through-holes include, for example, laser irradiation, etching, and mechanical drilling. Among these, laser irradiation is preferred. Laser irradiation can be performed using a suitable laser processing machine that uses a light source such as a carbon dioxide gas laser, a UV-YAG laser, or an excimer laser.

[0210] While there are no particular limitations on the shape of the via, it is generally circular (or slightly circular). The top diameter of the via is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. Here, the top diameter of the via refers to the opening diameter of the via on the surface of the redistribution layer.

[0211] (Step (F)) Step (F) is the step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring forming layer can be the same as the method of forming a conductor layer on an insulating layer in the manufacturing method of a printed wiring board. Furthermore, steps (E) and (F) can be repeated to alternately stack (build-up) the rewiring layer and the rewiring forming layer.

[0212] (Step (G)) Step (G) is the step of forming a solder resist layer on the rewiring layer. The solder resist layer can be made of any insulating material. From the viewpoint of ease of manufacturing semiconductor wafer packaging, photosensitive resins and thermosetting resins are preferred. Furthermore, the resin composition of this invention can be used as the thermosetting resin.

[0213] Furthermore, in step (G), bump machining can be performed as needed to form bumps. Bump machining can be performed by methods such as solder balls or solder plating. Furthermore, the formation of through holes in the bump machining can be performed in the same way as in step (E).

[0214] (Step (H)) The method for manufacturing a semiconductor wafer package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor wafer packages into individual semiconductor wafer packages for wafer individualization. There are no particular limitations on the method of dicing the semiconductor wafer package into individual semiconductor wafer packages.

[0215] <Semiconductor Device> A semiconductor device includes a semiconductor wafer package. Examples of semiconductor devices include various semiconductor devices provided for electrical products (e.g., computers, mobile phones, smartphones, tablet computers, wearable devices, digital cameras, medical devices, and televisions) and transportation vehicles (e.g., motorcycles, automobiles, trams, ships, and aircraft). [Example]

[0216] Hereinafter, embodiments are shown to specifically illustrate the present invention. However, the present invention is not limited to the embodiments described below. In the following description, the terms "parts" and "%" to indicate quantities, unless otherwise specified, refer to "parts by mass" and "% by mass," respectively. Furthermore, the operations described below, unless otherwise specified, are performed under normal temperature and pressure conditions.

[0217] <Preparation of Thermoplastic Resin Solution A> In a reaction vessel, add 69g of difunctional hydroxyl-terminated polybutadiene (Japan Soda Co., Ltd. "G-3000", number average molecular weight: 3000, hydroxyl equivalent: 1800g / eq.), 40g of aromatic hydrocarbon mixed solvent (Idemitsu Petrochemical Co., Ltd. "ipzole 150"), and 0.005g of dibutyltin laurate, and mix until uniformly dissolved. This yields a solution. Heat the solution to 60°C, and further add 8g of isophorone diisocyanate (Evonik Degussa Japan Co., Ltd. "IPDI", isocyanate group equivalent: 113g / eq.) while stirring, and react for approximately 3 hours. This yields the first reaction solution.

[0218] Next, 23g of cresol phenolic resin (DIC Corporation "KA-1160", hydroxyl equivalent: 117g / eq.) and 60g of ethyl diethylene glycol acetate (DAICEL Corporation) were added to the first reaction solution. The mixture was stirred and heated to 150°C for approximately 10 hours to obtain the second reaction solution. The disappearance of the NCO peak at 2250cm⁻¹ was confirmed by FT-IR. The disappearance of the NCO peak was considered the endpoint of the reaction, and the second reaction solution was cooled to room temperature. Then, the second reaction solution was filtered through a 100-mesh filter cloth. The filtrate yielded a solution containing thermoplastic resin A (polybutadiene resin containing phenolic hydroxyl groups) as a non-volatile component (non-volatile component 50% by mass; hereinafter referred to as "thermoplastic resin solution A"). The number-average molecular weight of thermoplastic resin A is 5900, and the glass transition temperature is -7℃.

[0219] <Preparation of Thermoplastic Resin Solution B> In a flask equipped with a stirrer, thermometer, and condenser, 368.41 g of ethyl diethylene glycol acetate and 368.41 g of "Solvesso 150" (registered trademark) (an aromatic solvent) manufactured by Exxon Mobil were added as solvents. Then, in the aforementioned flask, 100.1 g (0.4 moles) of diphenylmethane diisocyanate and 400 g (0.2 moles) of polycarbonate diol ("C-2015N" manufactured by Kuraray, number average molecular weight: approximately 2000, hydroxyl equivalent: 1000 g / eq., non-volatile components: 100% by mass) were added, and the mixture was reacted at 70°C for 4 hours. This yielded the first reaction solution.

[0220] Next, in the aforementioned flask, 195.9 g (0.2 mol) of nonylphenol phenolic resin (hydroxyl equivalent: 229.4 g / eq, average functionality: 4.27, average calculated molecular weight: 979.5 g / mole) and 41.0 g (0.1 mol) of ethylene glycol bis(triphenyl) anhydride were added. The mixture was heated to 150°C over 2 hours and allowed to react for 12 hours. This yielded the second reaction solution. The disappearance of the NCO peak at 2250 cm⁻¹ was confirmed by FT-IR. The disappearance of the NCO peak was considered the endpoint of the reaction, and the second reaction solution was cooled to room temperature. Then, the second reaction solution was filtered through a 100-mesh filter cloth. Thus, as the filtrate, a solution containing thermoplastic resin B (a polycarbonate resin containing phenolic hydroxyl groups) with reactive functional groups as a non-volatile component was obtained (non-volatile component 50% by mass; hereinafter referred to as "thermoplastic resin solution B"). The thermoplastic resin B has a number average molecular weight of 6100 and a glass transition temperature of 5°C.

[0221] [Example 1] <Preparation of Resin Coating A> Mix 3 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "jER828EL", epoxy equivalent: 184~194 g / eq.) as component (A), 1 part of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent: 276 g / eq.) as component (A), and 2 parts of epoxypropylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630", epoxy equivalent: 95 g / eq.) as component (A). The following components were prepared: 2 parts of cresol phenolic resin (DIC Corporation "KA-1160", phenolic hydroxyl equivalent: 117 g / eq.) as component (B-2); 1.54 parts of active ester resin (DIC Corporation "HPC-8000-65T", active group equivalent: approximately 223, toluene solution with 65% by mass of non-volatile components) as component (B-2); 4 parts of maleimide compound (Designer Moleculars "BMI-689") as component (B-1); 70 parts of inorganic filler A as component (C); 20 parts of thermoplastic resin solution A (non-volatile components: 50%) as component (D); 0.05 parts of curing accelerator (Shikoku Chemical Industry Co., Ltd. "1B2PZ") as component (E); and 15 parts of methyl ethyl ketone as solvent. The mixture was uniformly dispersed using a high-speed rotary mixer. This process is repeated to prepare the resin coating. Hereinafter, resin coatings prepared in this manner will be collectively referred to as "Resin Coating A".

[0222] Here, inorganic filler A is spherical silica (Admatechs "SO-C2") surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573"), with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m2 / g.

[0223] <Preparation of Resin Sheet B> As a support, a PET film (Toray Industries Ltd.'s "Lumirror R80"; thickness: 38μm, softening point: 130℃, sometimes referred to as "release PET") is prepared, with one side of the main surface treated with an alkyd resin-based release agent (Lintec Corporation's "AL-5").

[0224] Resin coating A, with a dried resin composition layer thickness of 100 μm, is uniformly applied to the release surface of the PET using a mold coating machine. Then, resin coating A is dried at 80°C to 120°C (average 100°C) for 6 minutes. This yields a resin sheet containing a support and a resin composition layer comprising the resin composition disposed on the support. Hereinafter, the resin sheet thus produced will also be referred to as "resin sheet B".

[0225] <Preparation of Evaluation Hardened Material C> A portion of resin sheet B is cut out and heated at 180°C for 90 minutes to thermally harden the resin composition layer. Afterward, the support is peeled off to obtain the evaluation hardened material. Hereinafter, the evaluation hardened material prepared in this way will also be referred to as "Evaluation Hardened Material C".

[0226] <Obtaining and Evaluating Various Parameters of Cured Resin Compositions> Using resin composition layers of resin sheet B or evaluation cured material C, various parameters of the cured resin composition are obtained, and evaluations are conducted from the perspective of warpage and long-term reliability, following the evaluation methods described later. Furthermore, using evaluation cured material C, evaluations are conducted from the perspective of chemical resistance, following the evaluation methods described later.

[0227] [Example 2] The inorganic filler A, which was component (A) in Example 1, was replaced with 115 parts of inorganic filler B. Here, as inorganic filler B, spherical alumina treated with "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., with a maximum cross-sectional diameter of 5 μm was used. The average particle size of inorganic filler B was measured to be 1.5 μm and the specific surface area was 2.0 m² / g. Except as described above, the same procedure as in Example 1 was followed to prepare a resin coating A containing a resin composition. Then, using resin coating A, the same procedure as in Example 1 was followed to obtain resin sheet B and evaluation hardened material C. The resin composition layer of resin sheet B and evaluation hardened material C were used in the same procedure as in Example 1, and the hardened material of the resin composition was evaluated.

[0228] [Example 3] The bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation "jER828EL"), 1 part of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000L"), and 2 parts of epoxypropylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation "630") used as component (A) in Example 1 were replaced with 2 parts of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation "jER828EL", epoxy equivalent: 184~194g / eq.), 2 parts of naphthalene type epoxy resin (manufactured by DIC Corporation "HP4032", epoxy equivalent: 135~165g / eq.), and 2 parts of biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation "YX4000", epoxy equivalent: about 185g / eq.). Furthermore, the following components were changed from 2 parts of cresol phenolic resin (DIC Corporation's "KA-1160"), 1.54 parts of active ester resin (DIC Corporation's "HPC-8000-65T"), and 4 parts of maleimide compound (Designer Moleculars' "BMI-689"), which were components (B-2) in Example 1, to 1 part of cresol phenolic resin (DIC Corporation's "KA-1160"), which were components (B-2), and 4 parts of maleimide compound (Designer Moleculars' "BMI-689"), which were components (B-1). Furthermore, 20 parts of thermoplastic resin solution A (non-volatile component: 50%), which was component (D) in Example 1, were replaced with 12 parts of thermoplastic resin solution A (non-volatile component: 50%) and 12 parts of thermoplastic resin solution B (non-volatile component: 50%), which was component (D). Also, 0.05 parts of curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ"), which was component (E) in Example 1, were replaced with 0.05 parts of curing accelerator (4-dimethylaminopyridine (DMAP)), which was component (E). Except for the above, the same procedure as in Example 1 was followed to prepare a resin coating A containing the resin composition. Then, using the resin coating A, the same procedure as in Example 1 was followed to obtain a resin sheet B and an evaluation cured product C. The resin composition layer of the resin sheet B and the evaluation cured product C were used in the same procedure as in Example 1, and the cured product of the resin composition was evaluated.

[0229] [Comparative Example 1] The bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "jER828EL"), 3 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000L"), and 2 parts of epoxypropylamine type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "630") used as component (A) in Example 1 were replaced with 1 part of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "jER828EL", epoxy equivalent: 184~194 g / eq.), 6 parts of naphthalene type epoxy resin (manufactured by DIC Co., Ltd. "HP4032", epoxy equivalent: 135~165 g / eq.) and 1 part of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent: 276 g / eq.). Furthermore, the following components were changed from component (B-2) in Example 1: 2 parts of cresol phenolic resin (DIC Corporation, "KA-1160"), 1.54 parts of reactive ester resin (DIC Corporation, "HPC-8000-65T"), and 4 parts of maleimide compound (Designer Moleculars, "BMI-689"), to 4.62 parts of reactive ester resin (DIC Corporation, "HPC-8000-65T"), and component (B-1). Component (B-1) was not used. Furthermore, the 70 parts of inorganic filler A (C) in Example 1 were changed to 60 parts of inorganic filler A. Furthermore, 20 parts of thermoplastic resin solution A (non-volatile component: 50%), which was component (D) in Example 1, were replaced with 16 parts of thermoplastic resin solution B (non-volatile component: 50%), which was component (D). Also, 0.05 parts of curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ"), which was component (E) in Example 1, were replaced with 0.10 parts of curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ"). Except for the above, the same procedure as in Example 1 was followed to prepare a resin coating A containing the resin composition. Then, using the resin coating A, the same procedure as in Example 1 was followed to obtain a resin sheet B and an evaluation cured product C. The resin composition layer of the resin sheet B and the evaluation cured product C were used in the same procedure as in Example 1, and the cured product of the resin composition was evaluated.

[0230] [Comparative Example 2] The bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "jER828EL"), 3 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000L"), and 2 parts of epoxypropylamine type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "630") used as component (A) in Example 1 were changed to 1 part of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "jER828EL", epoxy equivalent: 184~194 g / eq.), 4 parts of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent: 276 g / eq.), and 2 parts of biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "YX4000", epoxy equivalent: about 185 g / eq.). Furthermore, the components of cresol phenolic resin (DIC Corporation "KA-1160", phenolic hydroxyl equivalent: 117 g / eq.) used as component (B-2) in Example 1, 1.54 parts of reactive ester resin (DIC Corporation "HPC-8000-65T") used as component (B-2), and 4 parts of maleimide compound (Designer Moleculars "BMI-689") used as component (B-1), were changed to 2 parts of cresol phenolic resin (DIC Corporation "KA-1160", phenolic hydroxyl equivalent: 117 g / eq.) used as component (B-2) and 6.16 parts of reactive ester resin (DIC Corporation "HPC-8000-65T") used as component (B-2). Component (B-1) was not used. Furthermore, the 70 parts of inorganic filler A, which was component (C) in Example 1, were replaced with 50 parts of inorganic filler A. Furthermore, instead of 20 parts of thermoplastic resin solution A (non-volatile component: 50%), which was component (D) in Example 1, 5.71 parts of an epoxy-containing phenoxy resin (Mitsubishi Chemical Corporation "YX7200B35", epoxy equivalent: 3000~16000 g / eq., non-volatile component: 35%) were used. The 0.05 parts of curing accelerator (Shikoku Chemical Industry Co., Ltd., "1B2PZ"), which was component (E) in Example 1, were replaced with 0.10 parts of curing accelerator (Shikoku Chemical Industry Co., Ltd., "1B2PZ"). Except for the above, the same procedure as in Example 1 was followed to prepare a resin coating A containing the resin composition. Then, using resin coating A, the process was carried out in the same manner as in Example 1 to obtain resin sheet B and evaluation hardened material C. The resin composition layer of resin sheet B and evaluation hardened material C were carried out in the same manner as in Example 1, and the hardened resin composition was evaluated.

[0231] [Comparative Example 3] The bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "jER828EL"), 3 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000L"), and 2 parts of epoxy propylamine type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "jER630") used as component (A) in Example 1 were replaced with 2 parts of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "jER828EL", epoxy equivalent: 184~194 g / eq.), 1 part of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent: 276 g / eq.) and 1 part of epoxy propylamine type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "630", epoxy equivalent: 95 g / eq.). Furthermore, the following components were changed from component (B-2) in Example 1: 2 parts of cresol phenolic resin (DIC Corporation "KA-1160"), 1.54 parts of reactive ester resin (DIC Corporation "HPC-8000-65T"), and 4 parts of maleimide compound (Designer Moleculars "BMI-689"), to component (B-2): 2 parts of cresol phenolic resin (DIC Corporation "KA-1160", phenolic hydroxyl equivalent: 117 g / eq.) and 1.54 parts of reactive ester resin (DIC Corporation "HPC-8000-65T"), respectively. Component (B-1) was not used. Furthermore, the 70 parts of inorganic filler A (C) in Example 1 were changed to 40 parts of inorganic filler A. Furthermore, 20 parts of thermoplastic resin solution A (non-volatile component: 50%), which was component (D) in Example 1, were changed to 32 parts of thermoplastic resin solution A (non-volatile component: 50%). Except as described above, a resin coating A containing the resin composition was prepared in the same manner as in Example 1. Then, using the resin coating A, in the same manner as in Example 1, a resin sheet B and an evaluation cured product C were obtained. The resin composition layer of the resin sheet B and the evaluation cured product C were then evaluated in the same manner as in Example 1.

[0232] [Evaluation Method] Using the resin composition layer of resin sheet B obtained in the above examples and comparative examples, or the evaluation hardened material C, various parameters were obtained for the hardened material of the resin composition, and the following method was used to evaluate it from the viewpoints of heat resistance, warpage, and long-term reliability. Furthermore, using the evaluation hardened material C, the following method was used to evaluate it from the viewpoint of chemical resistance. In addition, Table 1 records the parameters used for evaluation among the obtained parameters. The evaluation results are shown in Table 1.

[0233] <Obtaining Various Parameters> (Determination of Average Linear Thermal Expansion Coefficient (CTE) α) The hardened material C used for evaluation was cut into pieces approximately 5 mm wide and 15 mm long to obtain test pieces D. For test pieces D, thermomechanical analysis was performed using a thermomechanical analysis apparatus (Rigaku Corporation's "Thermo Plus TMA8310") via the tensile-weight method. Specifically, after mounting test piece D onto the aforementioned thermomechanical analysis apparatus, the coefficient of thermal expansion was measured twice consecutively under the conditions of a load of 1 g and a heating rate of 5 °C / min. Then, based on the results of the second measurement, the average linear thermal expansion coefficient α (ppm / K) in the range from 25 °C (298 K) to 150 °C (423 K) was calculated.

[0234] (Determination of dynamic elastic modulus; acquisition of glass transition temperature Tg, storage modulus E', and crosslinking density n) The hardened material C used for evaluation was cut into pieces 5 mm wide and 15 mm long to obtain test pieces E. For this test piece E, a viscoelasticity measuring device (Hitachi Advanced Technology Co., Ltd. "DMA7100") was used to perform thermomechanical analysis by tensile-weighted method. Specifically, after the test piece E was mounted on the aforementioned thermomechanical analysis device, the storage modulus and loss modulus were measured under the conditions of a load of 200 mN and a heating rate of 5 °C / min.

[0235] First, the glass transition temperature Tg (°C) is obtained from the peak of tanδ (the curve of the ratio of storage modulus to loss modulus as a function of temperature), which is obtained as a measurement result.

[0236] Next, the specified temperature T (K) is determined. Specifically, the specified temperature T (K) is determined by converting the obtained glass transition temperature Tg (°C) to K, adding 273 K, and then adding 80 K. Furthermore, since the storage modulus value tends not to vary significantly in the temperature range near the specified temperature T (K), an error within the range of -5°C to +5°C is allowed for the determined specified temperature T (K). Then, the measured value E' (unit: GPa, i.e., 109 Pa) of the storage modulus at the determined specified temperature T (K) is obtained.

[0237] Next, the crosslinking density n (mol / cm3) is calculated by substituting the obtained storage modulus E' (Pa) into the following formula. Here, the crosslinking density n can be considered as an index representing the number of crosslinked molecules present per unit volume. n = E' / 3RT (in the above formula, T is the specified temperature T (K), E' is the measured value of the storage modulus (Pa) at the specified temperature T (K), and R is 8310000 (pa･cm3 / mol･K) as a gas constant. In addition, as E' / 3, the measured value of the shear elastic modulus G' (109 Pa) at the specified temperature T (K) can be used.

[0238] (Obtaining the value Zf) The value Zf is defined as the value obtained by dividing the average linear thermal expansion coefficient α (ppm / K) of the cured material by the crosslinking density n (mol / cm3) of the cured material. This value Zf (ppm·cm3 / mol·K) is obtained as a parameter of the cured material of the resin composition. By comparing the obtained value Zf with the evaluation results of the various assessments described below, the scope of the problems that can be solved in this invention is explored.

[0239] <Long-term reliability assessment> Long-term reliability assessment is carried out by performing an HTS test on the cured resin composition, measuring the breaking strength before and after the HTS test, and calculating the change in breaking strength (%).

[0240] (HTS Test) The hardened material C for evaluation is subjected to an HTS test (High Thermal Storage test). In the HTS test, the hardened material C for evaluation is maintained at 150°C for 1000 hours. Thus, the hardened material C' for evaluation after the HTS test is obtained.

[0241] (Determination of breaking strength before and after HTS test) Five test pieces F were obtained by cutting a dumbbell shape (No. 1) from the evaluation hardened material C. Similarly, five test pieces F' were obtained by cutting a dumbbell shape (No. 1) from the evaluation hardened material C'. Tensile tests were performed on each test piece F and F' using an ORIENTEC RTC-1250A tensile testing machine at 23°C and a test speed of 5 mm / min. The tensile breaking strength (hereinafter referred to as "breaking strength") was determined from the stress-strain curve. The determination was performed according to JIS K7127:1999. The average breaking strength of the five test pieces F was defined as the tensile breaking strength σ0 before the HTS test. The average breaking strength of the five test pieces F' was defined as the tensile breaking strength σ1 after the HTS test. (Calculation of Change (%)) Next, the change (%) of tensile breaking strength before and after the HTS test is calculated based on the following formula: Change (%) = {(σ1-σ0) / σ0} × 100 (Evaluation) The change (%) obtained as above is evaluated according to the following criteria. "○": When the change (%) is in the range of -10% to +10%, the change is small and the long-term reliability is excellent. "×": The change (%) is not in the range of -10% to +10%, the change is large and the long-term reliability is poor. Furthermore, if the test piece F' of Comparative Example 3 is observed and evaluated as having poor long-term reliability, it is considered to be deterioration caused by oxidation.

[0242] <Warpage Assessment> (Fabrication of Silicon Wafer with Insulating Layer for Warpage Measurement) A resin sheet B was laminated onto one side of a 12-inch disk-shaped silicon wafer (775 μm thick) using a batch vacuum pressure laminator (Nikko Materials CVP700, a two-stage stacking laminator). The support was then removed. The same process was repeated twice more on top of the resin sheet laminated to the silicon wafer, involving the lamination of the resin sheet and the removal of the support. This resulted in a 300 μm thick laminate of resin layers consisting of a total of three layers on the silicon wafer. The resulting silicon wafer with the resin-coated laminate was then heat-treated in an oven at 180°C for 90 minutes. This yields a silicon wafer with a resin-coated layer (i.e., a silicon wafer with an insulating layer) that has undergone curing. (Measurement of Warpage) With one end of the obtained silicon wafer with the insulating layer pressed against a flat platform, the vertical distance between the lower part of the end of the silicon wafer with the insulating layer and the upper part of the platform is measured as the warpage. The end showing the maximum warpage (μm) is defined. (Evaluation) The maximum warpage (μm) defined above is evaluated according to the following criteria: "○": When the maximum warpage is in the range of 0μm to 2000μm, the warpage is small and the warpage is sufficiently suppressed. "×": When the maximum warpage exceeds 2000μm, the warpage is large and the warpage is not sufficiently suppressed.

[0243] <Evaluation of Drug Resistance> (Drug Impregnation Test) Multiple test pieces G were obtained by cutting the hardened material C used for evaluation into squares with sides of 15 cm. Test pieces G were impregnated in a strong alkaline aqueous solution at 70°C for 1 hour. A 1% by mass potassium hydroxide aqueous solution was used as the strong alkaline aqueous solution. Afterwards, test pieces G were removed, washed with distilled water, and dried in an oven at 130°C for 1 hour. This yielded test piece G' after the drug impregnation test.

[0244] (Determination of mass before and after drug immersion test and calculation of mass reduction rate) The mass of test tablet G is measured and defined as the mass M0 before the drug immersion test. The mass of test tablet G' is also measured and defined as the mass M1 before the drug immersion test. Next, the mass reduction rate (%) before and after the drug immersion test is calculated based on the following formula: Mass reduction rate (%) = {(M0-M1) / M0} × 100 (Evaluation) The mass reduction rate (%) obtained above is evaluated according to the following criteria. "○": When the mass reduction rate (%) is less than 1% by mass, the amount of drug dissolved is very small, and the drug resistance is excellent. "×": When the mass reduction rate (%) is 1% or more by mass, the amount of drug dissolved is large, and the drug resistance is poor.

[0245] [Results] The results of the above examples and comparative examples are shown in Table 1 below. In Table 1 below, the amount of each component represents the converted amount of non-volatile components. Also, the "Inorganic Filler Content Ratio" shown in Table 1 shows the content of component (C) when the resin component in the resin composition is defined as 100% by mass. Also, α represents the average linear thermal expansion coefficient, T represents the specified temperature, E' represents the storage modulus at the specified temperature T, n represents the crosslinking density, Zf represents the value obtained by dividing the average linear thermal expansion coefficient α by the storage modulus E' at the specified temperature T, and Tg represents the glass transition temperature.

[0246]

[0247] <Exploration> As can be seen from Table 1, by comparing the examples and the comparative examples, it can be seen that in the examples, the resin composition containing components (A) and (B) has a value Zf (ppm･cm3 / mol･K) obtained by dividing the average linear thermal expansion coefficient α (ppm / K) of the cured material by the crosslinking density n (mol / cm3) of the cured material, which satisfies the following formula: 145<Zf<1300, and there is a tendency to provide a resin composition that can obtain a cured material with suppressed warpage and excellent long-term reliability.

[0248] Furthermore, it is also known that by satisfying the above formula with the value Zf, a resin composition that yields a cured product with excellent chemical resistance can be provided. Also, it is known that a cured product of the resin composition of the embodiments, a cured product of the resin composition, a resin film, a printed wiring board, a semiconductor wafer package, and a semiconductor device can also be provided.

[0249] Furthermore, it was confirmed that even when components (C) to (E) were not present in Examples 1 to 3, although the degree of difference was different, the results were still the same as those in the above examples. Also, it was confirmed that even when the strong alkaline aqueous solution used for drug resistance assessment in Examples 1 to 3 was replaced with any one of tetramethylammonium hydroxide solution, sodium hydroxide aqueous solution, or sodium carbonate aqueous solution instead of potassium hydroxide aqueous solution, the results were still the same as those in the above examples.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) a curing agent and (C) an inorganic filler, wherein when the non-volatile components in the resin composition are defined as 100% by mass, the content of component (C) is 50% by mass or more, and component (B) comprises a maleimine compound as shown in the following general formula (B2), (in general formula (B2), M1 each independently represents a divalent aliphatic hydrocarbon group containing a substituent alkyl group having 5 or more carbon atoms, and A each independently represents a divalent group containing a substituent alkyl group having 5 or more carbon atoms or a substituent aromatic ring; t represents an integer from 1 to 10); the average linear thermal expansion coefficient α (ppm / K) of the cured product obtained by curing the resin composition at 180°C for 90 minutes is divided by the crosslinking density n (mol / cm3) of the cured product, and the value Zf (ppm･cm3 / mol･K) satisfies the following formula: 145<Zf<1300.

2. The resin composition of claim 1, wherein the maleimine compound containing an aliphatic structure comprises a maleimine compound represented by the following general formula (B2-1), or a maleimine compound represented by the following general formula (B2-2), (in general formula (B2-1), M2 and M3 each independently represent an alkyl group having 5 or more carbon atoms that may have substituents, R30 each independently represents an oxygen atom, an aryl group, an alkyl group, or a divalent group formed by a combination of 2 or more of these groups; t1 represents an integer from 1 to 10); (in general formula (B2-2), M4, M6 and M7 each independently represent an alkyl group having 5 or more carbon atoms that may have substituents, M5 each independently represents a divalent group having an aromatic ring that may have substituents, R31 and R32 each independently represent an alkyl group having 5 or more carbon atoms; t2 represents an integer from 0 to 10, u1 and u2 each independently represent an integer from 0 to 4).

3. As in the resin composition of claim 1, wherein when the non-volatile components in the resin composition are defined as 100% by mass, the content of component (B) is 0.5% by mass or more.

4. As in the resin composition of claim 1, wherein when the non-volatile components in the resin composition are defined as 100% by mass, the content of component (C) is 60% by mass or more.

5. As in claim 1, where the non-volatile components in the resin composition are defined as 100% by mass, the content of component (C) is 70% by mass or more.

6. The resin composition of claim 1, wherein it further comprises (D) a thermoplastic resin.

7. The resin composition of claim 4, wherein component (D) has a functional group selected from the group consisting of hydroxyl, carboxyl, amino, vinyl, acrylonitrile and methacryl.

8. As in the resin composition of claim 4, wherein when the non-volatile components in the resin composition are defined as 100% by mass, the content of component (D) is 0.5% by mass or more and 25% by mass or less.

9. The resin composition of claim 1, wherein the average linear thermal expansion coefficient α of the aforementioned cured material is 25 ppm / K or less.

10. The resin composition of claim 1, wherein the crosslinking density n of the aforementioned cured material is 0.15 mol / cm3 or less.

11. The resin composition of claim 1, wherein the aforementioned value Zf satisfies the following formula: 150≦Zf≦1000.

12. The resin composition of claim 1 is for forming an insulating layer.

13. The resin composition of claim 1 is used for forming a solder resist layer.

14. A cured product of a resin composition as claimed in any one of claims 1 to 13.

15. A resin sheet comprising a support and a resin composition layer disposed on the support, the resin composition layer comprising a resin composition as claimed in any one of claims 1 to 13.

16. A printed wiring board comprising an insulating layer formed by a cured resin composition of any one of claims 1 to 13 or a cured resin composition of claim 12.

17. A semiconductor wafer package comprising a printed wiring board as claimed in claim 16 and a semiconductor wafer mounted on the printed wiring board.

18. A semiconductor wafer package comprising a semiconductor wafer and a cured resin composition of any one of claims 1 to 13 or a cured resin composition of claim 14 encapsulating the semiconductor wafer.

19. A semiconductor device comprising a printed wiring board as claimed in claim 16, or a semiconductor wafer package as claimed in claim 17 or 18.