Resin composition

Abstract

To provide a resin composition capable of obtaining a cured material excellent in crack resistance after a desmear treatment.SOLUTION: A resin composition including (A) a styrene-based and / or hydrogenated styrene-based polymers with a weight average molecular weight of 10,000 or less, (B) epoxy resins, (C) active ester compounds, and (E) radical polymerizable compounds, wherein (E) the radical polymerizable compounds include (E1) maleimide compounds, (E1) the maleimide compounds include maleimide compounds containing (E1-2) a trimethylindane skeleton, the content of component (A) is 1 mass% or more and 30 mass% or less relative to 100 mass% of resin components in the resin composition, the content of component (B) is 10 mass% or more and 60 mass% or less relative to 100 mass% of resin components in the resin composition, and the content of component (C) is 30 mass% or more and 70 mass% or less relative to 100 mass% of resin components in the resin composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition containing an epoxy resin. Further, it relates to a cured product, a sheet-like laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

Background Art

[0002] As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated is known. In the manufacturing method by the build-up method, generally, the insulating layer is formed by curing a resin composition. In recent years, further improvement in dielectric properties such as the dielectric constant of the insulating layer and further improvement in copper adhesion have been demanded.

[0003] Heretofore, as a resin composition for forming an insulating layer, by using an epoxy resin composition blended with an active ester compound instead of a general phenolic curing agent, it has been known that the dielectric tangent of the insulating layer can be suppressed to be lower (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, when an active ester compound is used, although the dielectric tangent can be suppressed to be lower, there is a tendency that cracks are likely to occur after desmear treatment.

[0006] An object of the present invention is to provide a resin composition capable of obtaining a cured product capable of suppressing the occurrence of cracks after desmear treatment.

Means for Solving the Problems

[0007] To achieve the object of the present invention, the inventors have conducted intensive studies. As a result, by using an epoxy resin and an active ester compound as components of the resin composition, and further containing a styrenic polymer and / or a hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less, surprisingly, it has been found that a cured product capable of suppressing the generation of cracks after desmear treatment can be obtained, and the present invention has been completed.

[0008] That is, the present invention includes the following contents. [1] (A) A resin composition containing a styrenic and / or hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. [2] The resin composition according to [1] above, wherein the component (C) has a carbon-carbon double bond. [3] The resin composition according to [1] or [2] above, wherein the component (C) contains an active ester compound containing a styryl group and a naphthalene structure. [4] The resin composition according to any one of [1] to [3] above, further containing (E) a radically polymerizable compound. [5] The resin composition according to [4] above, wherein the (E) radically polymerizable compound contains (E1) a maleimide compound. [6] The resin composition according to [5] above, wherein the (E1) maleimide compound contains (E1-2) a maleimide compound containing a trimethylindane skeleton. [7] The resin composition according to any one of [1] to [6] above, further containing (D) an inorganic filler. [8] The resin composition according to any one of [1] to [7] above, which is used for forming an interlayer insulating layer of a printed wiring board. [9] A cured product of the resin composition according to any one of [1] to [8] above.

[10] A sheet-like laminated material containing the resin composition according to any one of [1] to [8] above.

[11] A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of [1] to [8] above provided on the support.

[12] A printed wiring board including an insulating layer made of a cured product of the resin composition according to any one of [1] to [8] above.

[13] A semiconductor device including the printed wiring board according to

[12] above.

Advantages of the Invention

[0009] According to the present invention, there can be provided a resin composition capable of obtaining a cured product excellent in crack resistance after desmear treatment; a cured product of the resin composition; a sheet-like laminated material and a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device containing a cured product of the resin composition.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0011] In the following description, the amount of each component is the amount of the non-volatile component unless otherwise specified. In the following description, the "non-volatile component in the resin composition" may include (D) an inorganic filler unless otherwise specified, and the "resin component" refers to the component excluding (D) the inorganic filler among the non-volatile components contained in the resin composition unless otherwise specified.

[0012] <Resin Composition> The resin composition of the present invention contains (A) a styrenic and / or hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product excellent in crack resistance after desmear treatment can be obtained. Further, in the present invention, usually, a cured product having a low dielectric tangent and a low relative permittivity in both a room temperature to normal temperature range such as 23°C and a high temperature environment such as 90°C, and a high glass transition temperature can also be obtained.

[0013] The resin composition of the present invention may further contain an optional component in addition to (A) a styrenic and / or hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. Examples of the optional component include (D) an inorganic filler, (E) a radically polymerizable compound, (F) other curing agents, (G) a curing accelerator, (H) other additives, and (K) an organic solvent. In this specification, each of the components (A) to (K) may also be referred to as the “component (A)”, “component (B)”, etc. respectively. Hereinafter, each component contained in the resin composition will be described in detail.

[0014] <(A) Styrenic and / or hydrogenated styrenic polymer having a weight average molecular weight of 10,000 or less> The styrenic and / or hydrogenated styrenic polymer used in the present invention is not particularly limited as long as it is a styrenic polymer and / or hydrogenated styrenic polymer having a weight average molecular weight (Mw) of 10,000 or less, and may further contain monomers such as styrene and hydrogenated styrene. In this specification, the component (A) may sometimes be simply referred to as the “styrenic and / or hydrogenated styrenic polymer”.

[0015] Styrene-based and / or hydrogenated styrene-based polymers having such molecular weights have relatively low molecular weights, so they have low melt viscosities, excellent resin flowability of the resin composition, and can improve moldability. Furthermore, due to their relatively low molecular weights, although they are styrene-based and / or hydrogenated styrene-based polymers with a hydrophobic backbone, they exhibit high solubility not only in hydrophobic solvents such as toluene and hexane but also in polar solvents such as methyl ethyl ketone. Therefore, a varnish-like resin composition (resin varnish) can be easily prepared using methyl ethyl ketone with the above maleimide compound having a polar group. Also, since it is a styrene-based and / or hydrogenated styrene-based polymer, the dielectric properties of the resin composition can be improved.

[0016] As the styrene-based and / or hydrogenated styrene-based polymers used in this embodiment, conventionally known ones can be widely used and are not particularly limited. Specifically, for example, polymers or copolymers obtained by polymerizing or copolymerizing one or more of styrene-based monomers such as styrene, hydrogenated styrene, styrene derivatives, α-methylstyrene (where some hydrogen atoms of the benzene ring in styrene are substituted with alkyl groups), styrene where some hydrogen atoms of the vinyl group in styrene are substituted with alkyl groups, vinyltoluene, and isopropenyltoluene, and their hydrogenated products can be mentioned.

[0017] Specifically, as the styrene-based and / or hydrogenated styrene-based polymers, for example, those having structures represented by the following formulas (A-1) and (A-2) and their hydrogenated compounds are preferable examples.

[0018]

Chemical formula

[0019]

Chemical formula

[0020] In the above formulas (A-1) and (A-2), R 35 ~R 37may each independently be the same group or different groups, and each represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. Specifically, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, etc. may be mentioned.

[0021] Further, as the styrene-based and / or hydrogenated styrene-based copolymer, it is also possible to use a copolymer obtained by copolymerizing one or more styrene-based monomers and one or more other monomers copolymerizable therewith. The copolymerizable monomers may be aliphatic hydrocarbons, aromatic hydrocarbons, or a combination thereof, and examples thereof include unsaturated compounds such as olefins and non-conjugated dienes such as α-pinene, β-pinene, and dipentene.

[0022] For example, the styrene-based and / or hydrogenated styrene-based polymer can include a structure represented by the following formula (A-3).

[0023]

Chemical formula

[0024] R 38 is R 35 ~ R 37 represents the same group as

[0025] As such styrene-based and / or hydrogenated styrene-based polymers, commercially available products can also be used. For example, FTR6125 (styrene-aliphatic hydrocarbon copolymer, Mw 1950), FTR2140 (styrene-(α-methylstyrene) copolymer, Mw 3230), FTR0100 (α-methylstyrene polymer, Mw 1960), FTR8120 (styrene polymer, Mw 1420), etc. of the FTR (registered trademark) series manufactured by Mitsui Chemicals, Inc.; FMR0150 (styrene-aromatic hydrocarbon copolymer, Mw 2040), etc. of the FMR series manufactured by Mitsui Chemicals, Inc.; SX-100 (styrene polymer, Mw 2000), SG-100 (hydrogenated styrene-based polymer), SG-110 (hydrogenated styrene-based polymer), etc. manufactured by Yasuhara Chemical Co., Ltd. may also be used.

[0026] The above styrene-based and / or hydrogenated styrene-based polymers may be used alone or in combination of two or more.

[0027] The weight average molecular weight (Mw) of the styrene-based and / or hydrogenated styrene-based polymer used in this embodiment is 10,000 or less. By including a styrene-based and / or hydrogenated styrene-based polymer with Mw of 10,000 or less, a cured product excellent in crack resistance after desmear treatment can be obtained. Preferably, it is about 1000 to 9000. More preferably, it is 1000 to 7000, still more preferably, it is 1000 to 5000, and even more preferably, it is about 1000 to 4000. The weight average molecular weight of component (A) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

[0028] The content of component (A) is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1 to 1.0% by mass or more, still more preferably 3 to 3.0% by mass or more, even more preferably 4 to 4.0% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. Also, it is, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 8 to 8.0% by mass or less, still more preferably 6.5% by mass or less, even more preferably 5 to 5.0% by mass or less, particularly preferably 4.5% by mass or less. Specifically, when using a non-hydrogenated styrene-based polymer, these contents are suitable. When using a hydrogenated styrene-based polymer, these contents may be used, but preferably, for example, 2 to 4% by mass, preferably 2.5 to 3% by mass.

[0029] The content of component (A) is, for example, 1% by mass or more, 1.5% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 13% by mass or more, even more preferably 15 to 15.0% by mass or more, particularly preferably 16 to 16.0% by mass or more, based on 100% by mass of the resin components in the resin composition. Also, it is, for example, 30% by mass or less, preferably 25% by mass or less, more preferably 23.5% by mass or less, still more preferably 20% by mass or less, even more preferably 18 to 18.0% by mass or less. Specifically, when using a non-hydrogenated styrene-based polymer, these contents are suitable. When using a hydrogenated styrene-based polymer, these contents may be used, but preferably, for example, 3 to 15% by mass, preferably 5 to 10% by mass, more preferably 5.5 to 6% by mass.

[0030] <(B) epoxy resin> The resin composition of the present invention contains a (B) epoxy resin. The (B) epoxy resin means a curable resin having an epoxy group.

[0031] (B) Examples of the epoxy resin include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimide type epoxy resin, phenolphthalein type epoxy resin, etc. The (B) epoxy resin may be used alone or in combination of two or more.

[0032] The resin composition preferably contains, as the (B) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on 100% by mass of the non-volatile component of the (B) epoxy resin.

[0033] Epoxy resins include liquid epoxy resins (hereinafter sometimes referred to as "liquid epoxy resins") that are liquid at a temperature of 20°C and solid epoxy resins (hereinafter sometimes referred to as "solid epoxy resins") that are solid at a temperature of 20°C. The resin composition of the present invention may contain only a liquid epoxy resin as the epoxy resin, or may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin or a combination of a liquid epoxy resin and a solid epoxy resin, and more preferably a solid epoxy resin.

[0034] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0035] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferable.

[0036] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycerol-type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine-type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene-type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600", "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like. These may be used alone or in combination of two or more.

[0037] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0038] Examples of the solid epoxy resin include a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol novolak type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenylethane type epoxy resin, a phenolphthalimide type epoxy resin, and a phenolphthalein type epoxy resin.

[0039] Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like. These may be used alone or in combination of two or more.

[0040] (B) When using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin / solid epoxy resin) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, still more preferably 1 or less.

[0041] (B) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., still more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0042] (B) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC) method.

[0043] (B) The content of the component is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and even more preferably 8.5% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, and is, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and even more preferably 9 to 9.0% by mass or less.

[0044] The content of component (B) is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, even more preferably 30% by mass or more, particularly preferably 32% by mass or more, based on 100% by mass of the resin component in the resin composition. Also, it is, for example, 60% by mass or less, preferably 55% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, even more preferably 40% by mass or less, particularly preferably 36% by mass or less.

[0045] <(C) Active ester compound> The resin composition of the present invention contains a (C) active ester compound. The (C) active ester compound may be used alone or in combination of two or more in any ratio, and the same applies to the following (C1) component and (C2) component. The (C) active ester compound may have a function of reacting with the (B) epoxy resin to crosslink the (B) epoxy resin. The (C) active ester compound may have a carbon-carbon unsaturated bond, and this unsaturated bond is preferably a carbon-carbon double bond, and may be, for example, the same as the carbon-carbon unsaturated bond of the following (C1) component.

[0046] (C) As the active ester compound, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0047] Specifically, as the (C) active ester compound, a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, at least one selected from a dicyclopentadiene type active ester compound and a naphthalene type active ester compound is more preferred, and a dicyclopentadiene type active ester compound is even more preferred. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferred. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

[0048] Commercially available products of the (C) active ester compound include, as the active ester compound containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC); as the active ester compound containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC); as the phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC), as the active ester compound which is an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound which is a benzoylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and as the active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.) and the like.

[0049] (C) The active ester group equivalent of the active ester compound is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

[0050] <(C1) Compound Containing Aromatic Ester Skeleton and Unsaturated Bond> (C) As the active ester compound, a (C1) compound containing an aromatic ester skeleton and an unsaturated bond (also referred to as the “(C1) component” in this specification) may also be used.

[0051] (C1) The component is preferably a compound represented by the following general formula (AE1-1). [Chemical Formula] (In the general formula (AE1-1), Ar 11 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar 12 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, Ar 13 each independently represents a divalent group consisting of a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination thereof. n represents an integer from 0 to 10.)

[0052] Ar 11Examples of the monovalent aromatic hydrocarbon group represented by include those obtained by removing one hydrogen atom from monocyclic aromatic compounds such as phenyl group, furanyl group, pyrrolyl group, thiophenyl group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridinyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, etc.; those obtained by removing one hydrogen atom from condensed ring aromatic compounds such as naphthyl group, anthracenyl group, phenalenyl group, phenanthrenyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, phthalazinyl group, pteridinyl group, coumarinyl group, indole group, benzimidazolyl group, benzofuranyl group, acridinyl group, etc.; and the like. Among them, a phenyl group is preferred.

[0053] Ar 12 Examples of the divalent aromatic hydrocarbon group represented by include an arylene group, an aralkylene group, etc., and an arylene group is preferred. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferred, an arylene group having 6 to 20 carbon atoms is more preferred, and an arylene group having 6 to 10 carbon atoms is even more preferred. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, etc. Among them, a phenylene group is preferred.

[0054] Ar 13 As, a divalent group composed of these combinations is preferred. Ar 13 Examples of the divalent aromatic hydrocarbon group represented by are the same as those of the divalent aromatic hydrocarbon group represented by Ar 12 Ar 13 Examples of the divalent aliphatic hydrocarbon group represented by are more preferably a divalent saturated aliphatic hydrocarbon group, preferably an alkylene group or a cycloalkylene group, and more preferably a cycloalkylene group.

[0055] ​As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferable, a cycloalkylene group having 3 to 15 carbon atoms is more preferable, and a cycloalkylene group having 5 to 10 carbon atoms is even more preferable. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and cycloalkylene groups represented by the following formulas (a) to (d). The cycloalkylene group represented by the formula (c) is preferable. [Chemical formula] (In the formulas (a) to (d), "*" represents a bond.)

[0056] Ar 11 The monovalent aromatic hydrocarbon group represented by, Ar 12 The divalent aromatic hydrocarbon group represented by, and Ar 13 Examples of the substituent that the divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group represented by may have include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and the like. The substituents may be included alone or in combination of two or more. The substituent of Ar 11 Preferably contains an unsaturated bond among them.

[0057] When the compound represented by the general formula (AE1-1) is an oligomer or a polymer, n represents the average value thereof.

[0058] Specific examples of the component (C1) include the following compounds. Further, specific examples of the component (C1) include the compounds described in paragraphs 0068 to 0071 of International Publication No. 2018 / 235424 and paragraphs 0113 to 0115 of International Publication No. 2018 / 235425. In the formula, s represents an integer of 0 or more, and r represents an integer of 1 to 10. [Chemical formula]

[0059] The weight average molecular weight of the component (C1) is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, and preferably 3000 or less, more preferably 2000 or less, still more preferably 1500 or less, from the viewpoint of remarkably obtaining the effects of the present invention. The weight average molecular weight of the component (C1) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0060] The active ester equivalent (unsaturated bond equivalent) of the component (C1) is preferably 50 g / eq or more, more preferably 100 g / eq or more, still more preferably 150 g / eq, and preferably 2000 g / eq or less, more preferably 1000 g / eq or less, still more preferably 500 g / eq or less, from the viewpoint of remarkably obtaining the effects of the present invention. The active ester equivalent (unsaturated bond equivalent) is the mass of the component (C1) containing 1 equivalent of unsaturated bonds.

[0061] <(C2) An active ester compound having at least any one of the groups represented by the following formulas (1) to (3)> As the (C) active ester compound, an active ester compound having at least any one of the groups represented by the following formulas (1) to (3) (also referred to as the “(C2) component” in the present specification) may also be used.

Chemical formula

[0062] As the (C2) component, a compound having at least any one of the groups represented by formulas (1) to (3) and having an active ester site capable of reacting with the (A) component can be used. As the (C2) component, it is preferable to have at least any one of the groups represented by formulas (1) to (3) at the terminal. As the (C2) component, both terminals may be different groups or both terminals may be the same group.

[0063] In the group represented by formula (1), the methyl group, in the group represented by formula (2), the phenyl group, and in the group represented by formula (3), the styrene moiety are each preferably bonded to either the ortho-position, meta-position, or para-position with respect to the bond represented by *, and more preferably bonded to the ortho-position.

[0064] (Component (C2) is preferably a compound represented by the following general formula (AE2-1).) [Chemical formula] (In general formula (AE2-1), Ar 11 each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3), and Ar 12 each independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar 13 each independently represents a divalent group composed of a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination thereof. a represents an integer from 1 to 6, and b represents an integer from 0 to 10.)

[0065] Ar 11 is preferably a group represented by formula (1) and a group represented by formula (2).

[0066] Ar 12 , and Ar 13 are each the same as Ar 12 and Ar 13 in general formula (AE1-1), respectively, but as the divalent aromatic hydrocarbon group represented by Ar 12 , and as the divalent aromatic hydrocarbon group and the substituent which the divalent aliphatic hydrocarbon group represented by Ar 13 may have, for example, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, etc. are mentioned. The substituents may be included alone or in combination of two or more.

[0067] Ar13 Examples of the divalent group composed of these combinations represented by [the divalent group] include a divalent group combining an optionally substituted divalent aromatic hydrocarbon group and an oxygen atom, preferably a divalent group combining an optionally substituted divalent aromatic hydrocarbon group and one or more oxygen atoms alternately, more preferably a divalent group combining a naphthylene group which may have one or more substituents and one or more oxygen atoms alternately, and even more preferably a naphthyloxy group which may have a substituent.

[0068] When the compound represented by the general formula (AE2-1) is an oligomer or a polymer, a represents the average value thereof. b is the same as n in the general formula (AE1-1), and 0 is preferred.

[0069] The component (C2) is preferably a compound represented by the general formula (AE2-2).

Chemical formula

[0070] Ar 21 , and Ar 22 are the same as Ar 11 , and Ar 12 in the general formula (AE2-1), respectively.

[0071] Ar 23 is the same as the optionally substituted divalent aromatic hydrocarbon group having the substituent of Ar 13 in the general formula (AE2-1). a1 is the same as a in the general formula (AE2-1).

[0072] The (C2) component is preferably a compound represented by the general formula (AE2-3).

Chemical formula

[0073] Ar 31 is the same as Ar in the general formula (AE2-1). a2 and c2 are the same as a and c1 in the general formula (AE2-1), respectively. 11

[0074] d preferably represents an integer from 1 to 5, more preferably an integer from 1 to 4.

[0075] (C2) component may be synthesized by a known method, for example, it can be synthesized by the method described in the following examples. The synthesis of the (C2) component can be carried out by the method described in, for example, International Publication No. 2018 / 235424, or International Publication No. 2018 / 235425.

[0076] From the viewpoint of significantly obtaining the effects of the present invention, the weight average molecular weight of the (C2) component is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, and preferably 4000 or less, more preferably 3000 or less, still more preferably 2500 or less. The weight average molecular weight of the (C2) component is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

[0077] The active ester equivalent (unsaturated bond equivalent) of the (C2) component is the same as that of the (C1) component.

[0078] ​When the quantitative ratio of component (B) to component (C) is such that the total value obtained by dividing the mass of the non-volatile component of component (B) by the epoxy equivalent is defined as a, and the total value obtained by dividing the mass of the non-volatile component of component (C) by the active ester group equivalent is defined as b, it is preferable that b / a is 1.0 or more, more preferably 1.01 or more, still more preferably 1.03 or more, even more preferably 1.05 or more, particularly preferably 1.06 or more. Also, it is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.2 or less, even more preferably 1.18 or less, particularly preferably 1.17 or less. By setting the quantitative ratio of component (B) to component (C) within such a range, the effects of the present invention can be easily obtained.

[0079] The content of component (C) is, for example, 3% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. Also, it is, for example, 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 12% by mass or less.

[0080] The content of component (C) is, for example, 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 42% by mass or more, based on 100% by mass of the resin components in the resin composition. Also, it is, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less.

[0081] <(D) Inorganic filler> The resin composition of the present invention may contain (D) an inorganic filler as an optional component. The (D) inorganic filler is contained in the resin composition in a particulate state. The (D) inorganic filler may be used alone or in any combination of two or more kinds.

[0082] (D) As the material of the inorganic filler, an inorganic compound is used. (D) As the material of the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. may be mentioned. Among these, silica is particularly preferred. As silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. may be mentioned. Also, spherical silica is preferred as silica. (D) The inorganic filler may be used alone or in combination of two or more in any ratio.

[0083] (D) Examples of commercially available products of the inorganic filler include, for example, "SP60-05", "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "MGH-005" manufactured by Taiheiyo Cement Corporation, etc.

[0084] (D) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle size of the (D) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (D) inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter thereof is used as the average particle size for measurement. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample is measured for the volume-based particle size distribution of the inorganic filler using a laser diffraction type particle size distribution measuring device with the wavelengths of the light sources used being blue and red and in a flow cell method, and the average particle size is calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0085] (D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, and particularly preferably 3 m 2 / g or more. The upper limit of the specific surface area of the (D) inorganic filler is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 50 m 2 / g or less, and particularly preferably 40 m 2 / g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multi-point method.

[0086] (D) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By being surface-treated, the moisture resistance and dispersibility of the (D) inorganic filler can be enhanced. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; methacryl-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; amino-based silane coupling agents such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; and other silane coupling agents.Examples of non-silane coupling - alkoxysilane compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc. Further, the surface treatment agent may be used alone or in combination of two or more kinds at an arbitrary ratio.;

[0087] Examples of commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl-based silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy-based silane coupling agent); "KBM-1403" (styryl-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic-based silane coupling agent); "KBM-5103" (acrylic-based silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino-based silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (acid anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling - alkoxysilane compound), etc.;

[0088] From the perspective of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass, and even more preferably surface-treated with 0.3% to 2% by mass.

[0089] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the perspective of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and even more preferably 0.5 mg / m 2 or less.

[0090] (D) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. etc. can be used.

[0091] Although the content of the (D) inorganic filler in the resin composition is not particularly limited, when the non-volatile components in the resin composition are 100% by mass, it can preferably be 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, and even more preferably 75% by mass or less. The lower limit of the content of the (D) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it can be, for example, 0% by mass or more, 1% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, etc., preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 73% by mass or more.

[0092] <(E) Radical polymerizable compound> The resin composition of the present invention may contain an (E) radical polymerizable compound as an optional component. The (E) radical polymerizable compound may be used alone or in any combination of two or more.

[0093] The type of the radical polymerizable compound is not particularly limited as long as it has one or more (preferably two or more) radical polymerizable unsaturated groups in one molecule. Examples of the radical polymerizable compound include compounds having one or more selected from maleimide group, vinyl group, allyl group, styryl group, vinylphenyl group, acryloyl group, methacryloyl group, fumaroyl group, and maleoyl group as the radical polymerizable unsaturated group. Among them, from the viewpoint of easily obtaining a cured product with excellent dielectric properties, it is preferable to contain an (E1) maleimide compound and / or an (E2) other radical polymerizable compound. The (E2) other radical polymerizable compound is a compound having no maleimide group and having a radical polymerizable unsaturated group other than the maleimide group, and among them, it is preferable to contain one or more selected from (meth)acrylic resins and styryl resins.

[0094] (E1) As long as the maleimide compound has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule, its type is not particularly limited. Examples of the maleimide compound include maleimide resins containing an aliphatic skeleton with 36 carbon atoms derived from dimer diamine, such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-689" (all manufactured by Dicna Molecules); maleimide resins containing an indane skeleton described in the Invention Association's Published Technical Report Public Technical Number 2020-500211; and maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT", "MIR-5000-60T" (both manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), "BMI-80" (manufactured by KAI Chemical Co., Ltd.).

[0095] (E1) Among them, it is preferable to contain a maleimide compound containing an indane skeleton (also referred to as "(E1-1) specific maleimide compound" in this specification), and it is more preferable to contain a maleimide compound containing a trimethylindane skeleton. (E1-1) The specific maleimide compound can be produced, for example, by the method described in the Invention Association's Published Technical Report Public Technical Number 2020-500211. According to the production method described in this Invention Association's Published Technical Report Public Technical Number 2020-500211, a maleimide compound with a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method contains a structure represented by the following formula (M1). Therefore, (E1) the maleimide compound may contain a maleimide compound containing a structure represented by the formula (M1).

[0096]

Chemical formula

[0097] (In the formula (M1), R 1each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R 2 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n 1 represents an average repeating unit number of 0.95 to 10.0; n 2 each independently represents an integer of 0 to 4; n 3 each independently represents an integer of 0 to 3. R 1 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R may be substituted with a halogen atom. R 2 The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R may be substituted with a halogen atom. n 2 When n is 2 to 4, R 1 may be the same or different within the same ring. n 3 When n is 2 to 3, R 2 may be the same or different within the same ring.)

[0098] In formula (M1), n 1 represents the average repeating unit number, and the range thereof is 0.95 to 10.0. According to the production method described in the Japan Institute of Invention and Innovation Publication Technical Report Publication No. 2020-500211, a group of maleimide compounds containing the structure represented by formula (M1) can be obtained. The average repeating unit number n in formula (M1) 1As can be seen from the fact that it can be less than 1.00, the maleimide compound containing the structure represented by the thus obtained formula (M1) may include a maleimide compound having 0 repeating units of the trimethylindane skeleton. Therefore, from the maleimide compound containing the structure represented by the formula (M1), by purification, a specific maleimide compound (E1-1) is obtained by removing the maleimide compound having 0 repeating units of the trimethylindane skeleton, and the resin composition may contain only the obtained (E1-1) specific maleimide compound. However, even when the maleimide compound having 0 repeating units of the trimethylindane skeleton is contained in the resin composition, the effects of the present invention can be obtained. Also, when purification is omitted, cost can be suppressed. Therefore, it is preferable that the resin composition contains a maleimide compound containing the structure represented by the formula (M1) without removing the maleimide compound having 0 repeating units of the trimethylindane skeleton.

[0099] In the formula (M), the average number of repeating units n 1 is preferably 0.95 or more, more preferably 0.98 or more, still more preferably 1.0 or more, particularly preferably 1.1 or more, and preferably 10.0 or less, more preferably 8.0 or less, still more preferably 7.0 or less, particularly preferably 6.0 or less. When the average number of repeating units n 1 is within the above range, the effects of the present invention can be remarkably obtained. In particular, the glass transition temperature of the resin composition can be effectively increased.

[0100] Examples of the structure represented by the formula (M1) include the following.

[0101]

Chemical formula

[0102] The maleimide compound containing the structure represented by the formula (M1) may further contain the structure represented by the following formula (M2). For example, in the maleimide compound containing the structure represented by the formula (M1), in the formula (M1), n 2is 3 or less, and when R is not bonded to two or more of the ortho- and para-positions of the benzene ring to which the maleimide group is bonded, the structure represented by the formula (M2) may be included in combination with the structure represented by the formula (M1). 1

[0103]

Chemical formula

[0104] The maleimide compound containing the structure represented by formula (M1) preferably has a molecular weight distribution Mw / Mn calculated by gel permeation chromatography (GPC) measurement in a specific range. The molecular weight distribution is a value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and is expressed as "Mw / Mn". Specifically, the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by formula (M1) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw / Mn of the maleimide compound containing the structure represented by formula (M1) is in the above range, the effects of the present invention can be significantly obtained.

[0105] Among the maleimide compounds containing a structure represented by formula (M1), the average number of repeating units, n 1 The amount of the maleimide compound having a structure represented by formula (M1) is preferably in a specific range. 1 The amount of the maleimide compound having a repeating unit number n of 0 can be expressed in area % based on the results of GPC measurement. In detail, in the chromatogram obtained by the GPC measurement, the average repeating unit number n of the maleimide compound having a structure represented by formula (M1) relative to the total area of ​​the peak of the maleimide compound can be expressed in area %. 1 The average number of repeating units, n, is calculated by the ratio (area%) of the peak area of ​​the maleimide compound with n = 0. 1 Specifically, the average repeating unit number n 1 The amount of the maleimide compound having an average repeating unit number n of 0 is preferably 32 area % or less, more preferably 30 area % or less, and further preferably 28 area % or less. 1 When the amount of the maleimide compound having a molecular weight of 0 is within the above range, the effects of the present invention can be significantly obtained.

[0106] The maleimide group equivalent of the maleimide compound containing the structure represented by the formula (M1) is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, particularly preferably 200 g / eq. or more, and preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, particularly preferably 800 g / eq. or less. The maleimide group equivalent represents the mass of the maleimide compound per equivalent of the maleimide group. When the maleimide group equivalent of the maleimide compound containing the structure represented by the formula (M1) is within the above range, the effects of the present invention can be remarkably obtained.

[0107] (E2) Among other radically polymerizable compounds, as the (meth)acrylic resin, as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, its type is not particularly limited. Here, the term "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group. Examples of the methacrylic resin include "(meth)acrylic resins" such as "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0108] As the styryl resin, as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule, its type is not particularly limited. Examples of the styryl resin include styryl resins such as "OPE-2St", "OPE-2St 1200", "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0109] The content of the (E) radically polymerizable compound in the resin composition may be 0% by mass, may be greater than 0% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, when the non-volatile components in the resin composition are 100% by mass, and for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 2 to 2.0% by mass or less.

[0110] When the content of the (E) radically polymerizable compound in the resin composition is based on 100% by mass of the resin component in the resin composition, it may be 0% by mass, may be greater than 0% by mass, preferably 0.1% by mass or more, more preferably 1% by mass or more, particularly preferably 1.5% by mass or more. Also, for example, it is 20% by mass or less, preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, particularly preferably 3.5% by mass or less.

[0111] <(F) Other curing agents> The resin composition of the present invention may contain (F) other curing agents as optional components. This (F) other curing agent does not include those corresponding to the above-mentioned (A) to (C) and (E) components. Similar to the above-mentioned (C) active ester compound, the (F) other curing agent may have a function as an epoxy resin curing agent that reacts with the (B) epoxy resin to cure the resin composition. The (F) other curing agent may be used alone or in combination of two or more.

[0112] Examples of the (F) other curing agent include phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. Among them, it is preferable to use one or more curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents.

[0113] As the phenolic curing agent, a curing agent having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. From the viewpoints of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferable, and a phenolic curing agent containing a triazine skeleton is more preferable. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenolic novolak resin containing a triazine skeleton is preferable. Specific examples of the phenolic curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by DIC Corporation, and the like.

[0114] As the carbodiimide-based curing agent, a curing agent having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of the carbodiimide-based curing agent include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xilylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylene carbodiimide), poly(tetramethylxylene carbodiimide), poly(methylenediphenylene carbodiimide), and poly[methylenebis(methylphenylene) carbodiimide]. Commercially available products of the carbodiimide-based curing agent include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd.; "Stabaxol P", "Stabaxol P400", "High Kazyl 510", etc. manufactured by Rhein Chemie Co., Ltd.

[0115] As the acid anhydride-based curing agent, a curing agent having one or more acid anhydride groups in one molecule can be used, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as a styrene-maleic acid resin copolymerized from styrene and maleic acid, and the like. Commercially available products of the acid anhydride-based curing agent include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd.; "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd.; "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Co., Ltd., and the like.

[0116] As the amine-based curing agent, a curing agent having one or more, preferably two or more, amino groups in one molecule can be used. As the amine-based curing agent, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. can be mentioned, among which aromatic amines are preferred. As the amine-based curing agent, primary amines or secondary amines are preferred, and primary amines are more preferred. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. 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)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents include, for example, "SEIKACURE-S" manufactured by Seika Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "Epicure W" manufactured by Mitsubishi Chemical Corporation; and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd.

[0117] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0118] Examples of cyanate ester-based curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which part of these cyanate resins is triazine-ized, and the like. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-ized to form trimers), etc., manufactured by Lonza Japan Co., Ltd.

[0119] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanurate, and the like.

[0120] (F) The active group equivalent of other curing agents is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent represents the mass of the curing agent per equivalent of the active group.

[0121] The quantitative ratio of the epoxy resin to the curing agent, that is, the quantitative ratio of component (B) to components (C) and (F), is such that when the sum of the values obtained by dividing the mass of the non-volatile component of component (B) by the epoxy equivalent is a, the sum of the values obtained by dividing the mass of the non-volatile component of component (C) by the active ester group equivalent is b, and the sum of the values obtained by dividing the mass of the non-volatile component of component (F) by the active group equivalent is c, it is preferably that (b + c) / a is 1.0 or more, more preferably 1.01 or more, still more preferably 1.1 to 1.10 or more, even more preferably 1.15 or more, particularly preferably 1.2 or more. Also, it is preferably 2.0 or less, more preferably 1.75 or less, still more preferably 1.5 or less, even more preferably 1.4 to 1.40 or less, particularly preferably 1.35 or less. By setting the quantitative ratio of the epoxy resin to the curing agent within such a range, the effects of the present invention can be easily obtained.

[0122] When the content of (F) other curing agent in the resin composition is based on 100% by mass of the non-volatile component in the resin composition, it may be 0% by mass, or may be greater than 0% by mass. Preferably it is 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less.

[0123] When the content of (F) other curing agent in the resin composition is based on 100% by mass of the resin component in the resin composition, it may be 0% by mass, or may be greater than 0% by mass. Preferably it is 0.1% by mass or more, more preferably 1.0% by mass or more, particularly preferably 4.0% by mass or more, and preferably 50% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less.

[0124] <(G) Curing accelerator> The resin composition of the present invention may contain (G) a curing accelerator as an optional component.

[0125] Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. (G) The curing accelerator may be used alone or in combination of two or more.

[0126] Examples of phosphorus-based hardening accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine;Aromatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenylether, etc. are included.;

[0127] Examples of urea-based curing accelerators include, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea], and the like.

[0128] Examples of guanidine-based curing accelerators include, for example, 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like.

[0129] Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

[0130] As the imidazole-based curing accelerator, commercially available products may be used. For example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Kogyo Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can be mentioned.

[0131] Examples of the metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc. Specific examples of the organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of the organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc.

[0132] Examples of the amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

[0133] As the amine-based hardening accelerator, commercially available products may be used. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. etc. can be mentioned.

[0134] The content of the (G) hardening accelerator in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the (E) hardening accelerator in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, for example, it can be 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, etc.

[0135] <(H) Other Additives> The resin composition of the present invention may further contain an optional additive as a non-volatile component. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; epoxy curing agents other than active ester compounds such as phenolic curing agents, naphthol-based curing agents, acid anhydride-based curing agents, thiol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, and imidazole-based curing agents; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic fillers such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic-based flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers, etc.(F) Other additives may be used alone or in combination of two or more in any ratio. (H) The content of other additives can be appropriately set by those skilled in the art.

[0136] <(K) Organic solvent> In addition to the non-volatile components described above, the resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component. (K) As the organic solvent, known ones can be appropriately used, and the type is not particularly limited. (K) Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (K) The organic solvent may be used alone or in combination of two or more in any ratio.

[0137] In one embodiment, the content of the (K) organic solvent is not particularly limited. When the total components in the resin composition are 100% by mass, for example, it can be 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, etc.

[0138] <Method for producing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) a styrene-based and / or hydrogenated styrene-based polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound, optionally (D) an inorganic filler, optionally (E) a radically polymerizable compound, optionally (F) other curing agents, optionally (G) a curing accelerator, optionally (H) other additives, and optionally (K) an organic solvent to an arbitrary preparation container in an arbitrary order and / or partially or entirely simultaneously and mixing them. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or throughout. Further, in the process of adding and mixing or thereafter, the resin composition may be stirred or shaken using a stirring device or a shaking device such as a mixer to be uniformly dispersed. Further, defoaming may be performed under low-pressure conditions such as under vacuum simultaneously with stirring or shaking.

[0139] <Properties of resin composition> The resin composition of the present invention contains (A) a styrene-based and / or hydrogenated styrene-based polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product excellent in crack resistance after desmear treatment can be obtained. Preferably, further, a cured product having a low dielectric tangent and a low relative permittivity in both a room temperature or normal temperature region such as 23°C and a high temperature environment such as 90°C, and a high glass transition temperature can be obtained.

[0140] The cured product of the resin composition of the present invention can have the characteristic of suppressing the occurrence of cracks after desmear treatment (roughening treatment). Therefore, in one embodiment, when 100 copper pad portions of the circuit board are observed after manufacturing and desmear treatment of the circuit board as in Test Example 2 below, the number of cracks can preferably be 10 or less (10% or less).

[0141] The cured product of the resin composition of the present invention can have the characteristic of having a low dielectric tangent (Df) even in a high-temperature environment such as 90°C. Therefore, in one embodiment, the dielectric tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 90°C as in Test Example 1 below can preferably be 0.020 or less, 0.010 or less, more preferably 0.009 or less, 0.008 or less, still more preferably 0.007 or less, 0.006 or less, particularly preferably 0.005 or less, 0.004 or less.

[0142] The cured product of the resin composition of the present invention can have the characteristic of having a low dielectric tangent (Df) even at room temperature or normal temperature such as 23°C. Therefore, in one embodiment, the dielectric tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23°C as in Test Example 1 below can preferably be 0.020 or less, 0.010 or less, more preferably 0.009 or less, 0.008 or less, still more preferably 0.007 or less, 0.006 or less, even more preferably 0.005 or less, 0.004 or less, particularly preferably 0.003 or less.

[0143] The cured product of the resin composition of the present invention can have the characteristic of having a low relative dielectric constant (Dk) even in a high-temperature environment such as 90°C. Therefore, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 90°C as in Test Example 1 below can preferably be 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less, and when containing hollow silica as the (D) inorganic filler, it can be further lowered, preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less, particularly preferably 3.0 or less.

[0144] The cured product of the resin composition of the present invention may have the characteristic of having a low relative dielectric constant (Dk) even at room temperature or normal temperature such as 23°C. Therefore, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23°C as in Test Example 1 below may preferably be 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less, and when containing hollow silica as the (D) inorganic filler, it can be made even lower, preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less, and particularly preferably 3.0 or less.

[0145] The cured product of the resin composition of the present invention may have the characteristic of having a high glass transition temperature. Therefore, in one embodiment, the glass transition temperature (Tg) of the cured product when thermally cured at 190°C for 90 minutes as in Test Example 3 below is preferably above 135°C, more preferably 140°C or higher, still more preferably 150°C or higher, and even more preferably 153°C or higher. The upper limit is not particularly limited and may be 200°C or less, etc., and such a glass transition temperature may apply, for example, when using a hydrogenated styrene-based polymer as the (A) component.

[0146] <Use of the resin composition> The resin composition of the present invention can be suitably used as a resin composition for insulation applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming the insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer (resin composition for forming an insulating layer for forming a conductor layer). Also, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention can also be widely used in applications where a resin composition is required, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, etc.

[0147] In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be preferably used as a resin composition for a rewiring formation layer as an insulating layer for forming a rewiring layer (a resin composition for forming a rewiring formation layer) and a resin composition for encapsulating a semiconductor chip (a resin composition for encapsulating a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the encapsulation layer. (1) A step of laminating a temporary fixing film on a substrate; (2) A step of temporarily fixing a semiconductor chip on the temporary fixing film; (3) A step of forming an encapsulation layer on the semiconductor chip; (4) A step of peeling the substrate and the temporary fixing film from the semiconductor chip; (5) A step of forming a rewiring formation layer as an insulating layer on the surface of the substrate and the temporary fixing film from which the semiconductor chip has been peeled, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0148] In addition, since the resin composition of the present invention provides an insulating layer with good component embedding properties, it can also be preferably used when the printed wiring board is a component-integrated circuit board.

[0149] <Sheet-like laminated material> The resin composition of the present invention can be used by coating it in a varnish state, but industrially, it is generally preferable to use it in the form of a sheet-like laminated material containing the resin composition.

[0150] As the sheet-like laminated material, the following resin sheets and prepregs are preferred.

[0151] In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

[0152] From the viewpoints of thinning the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can usually be 5 μm or more, 10 μm or more, etc.

[0153] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0154] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0155] When using a metal foil as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0156] The support may be subjected to a mat treatment, a corona treatment, or an antistatic treatment on the surface that joins the resin composition layer.

[0157] Further, as the support, a support with a release layer having a release layer on the surface that bonds to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, commercially available products may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., and the like.

[0158] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0159] In one embodiment, the resin sheet may further include an optional layer as needed. Examples of such an optional layer include a protective film similar to the support provided 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 for example, it is 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and scratches to the surface of the resin composition layer.

[0160] The resin sheet can be produced, for example, by directly using a liquid resin composition or preparing a resin varnish by dissolving the resin composition in an organic solvent, applying this on a support using a die coater or the like, and further drying to form a resin composition layer.

[0161] Examples of the organic solvent include the same ones as those described as components of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0162] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or the resin varnish, for example, when using a resin composition or a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0163] The resin sheet can be stored by winding it into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0164] In one embodiment, the prepreg is formed by impregnating a sheet-shaped fiber base material with the resin composition of the present invention.

[0165] The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

[0166] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0167] The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned resin sheet.

[0168] The sheet-shaped laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board).

[0169] <Printed Wiring Board> The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0170] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above-described resin sheet. (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of curing (for example, thermally curing) the resin composition layer to form an insulating layer

[0171] The "inner layer substrate" used in step (I) is a member that serves as a substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Further, the substrate may have a conductor layer on one or both sides thereof, and this conductor layer may be pattern-processed. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0172] The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). Note that it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate instead of directly pressing the thermocompression bonding member against the resin sheet.

[0173] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding 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, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under reduced pressure conditions of 26.7 hPa or less pressure.

[0174] The lamination can be carried out by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichco Materials Co., Ltd., a batch type vacuum pressure laminator, and the like.

[0175] After the lamination, under normal pressure (atmospheric pressure), for example, by pressing the thermocompression bonding member from the support side, a smoothing treatment of the laminated resin sheet may be performed. The pressing conditions for the smoothing treatment can be the same as the thermocompression bonding conditions for the above lamination. The smoothing treatment can be carried out by a commercially available laminator. Note that the lamination and the smoothing treatment may be continuously carried out using the above commercially available vacuum laminator.

[0176] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0177] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0178] For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition and the like. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0179] Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0180] When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art used for manufacturing printed wiring boards. When removing the support after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

[0181] In other embodiments, the printed wiring board of the present invention can be manufactured using the above-described prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

[0182] Step (III) is a step of drilling holes in the insulating layer, by which holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0183] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also carried out in this step (IV). The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0184] The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution as the alkaline solution. Commercially available swelling liquids include, for example, "Swelling Dip Security Gun P" and "Swelling Dip Security Gun SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0185] The oxidizing agent used for the roughening treatment is not particularly limited. For example, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0186] In addition, as the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferable. Examples of commercially available products include "Reduction Solution Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0187] The treatment with the neutralizing solution can be carried out by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0188] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited.

[0189] In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single-metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single-metal layer of copper is even more preferred.

[0190] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0191] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0192] In one embodiment, the conductor layer may be formed by plating. For example, by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0193] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Then, an unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0194] In another embodiment, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, it is preferable to perform step (V) between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventional known technique such as a subtractive method or a modified semi-additive method.

[0195] The metal foil can be manufactured by known methods such as an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., and the like.

[0196] <Semiconductor device> The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0197] Examples of the semiconductor device include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and airplanes).

Example

[0198] Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "mass %", respectively, unless otherwise specified. The temperature condition in the case where the temperature is not specified is room temperature (25 °C).

[0199] [Synthesis Example 1: Synthesis of Active Ester Compound A] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 203.0 g of isophthaloyl chloride (the number of moles of acid chloride groups: 2.0 moles) and 1400 g of toluene were charged, and the system was purged with nitrogen under reduced pressure and dissolved. Next, 113.9 g (0.67 mole) of ortho-phenylphenol and 240 g of a benzyl-modified naphthalene compound (the number of moles of phenolic hydroxyl groups: 1.33 moles) were charged, and the system was purged with nitrogen under reduced pressure and dissolved. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the temperature inside the system was controlled to 60 °C or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Then, stirring was continued for 1.0 hour under these conditions. After completion of the reaction, the mixture was allowed to stand and separated, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for 15 minutes, then allowed to stand and separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration to obtain Active Ester Compound A in the form of a toluene solution having a non-volatile content of 62% by mass. The active ester equivalent of the obtained Active Ester Compound A was 238 g / eq.

[0200] [Synthesis Example 2: Synthesis of Active Ester Compound B] Into a flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer, 165 g of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / equivalent (eq), softening point 85 °C), 134 g (1.0 mol) of orthoallylphenol, and 1200 g of toluene were charged, and the system was purged with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthaloyl chloride was charged, and the system was purged with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, and while performing a nitrogen gas purge treatment, the temperature inside the system was controlled to 60 °C or lower, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the addition was completed, stirring was carried out for 1.0 hour. After completion of the reaction, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained toluene layer, stirred for 15 minutes, and the aqueous layer was removed by standing and liquid separation. This operation was repeated until the pH of the aqueous layer reached 7. Then, by adjusting the non-volatile content to 70% by mass by heating and drying, an active ester resin represented by the following chemical formula was obtained. [Chemical formula]

[0201] In the above chemical formula, S is independently 0 or an integer of 1 or more, and the average value of r calculated from the charging ratio is 1. Also, the broken line in the chemical formula represents a structure obtained by the reaction of isophthaloyl chloride and the polyaddition reaction resin of phenol and / or orthoallylphenol. When the ester group equivalent of the obtained active ester resin was calculated from the charging ratio, it was 214 g / equivalent (eq.).

[0202] [Example 1] Naphthalene type epoxy resin (DIC "HP-4032-SS", epoxy equivalent 144g / eq.) 10 parts, naphthalene aralkyl type epoxy resin (Nippon Steel Chemical & Material Co., Ltd. "ESN-475V", epoxy equivalent 330g / eq.) 5 parts, biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC-3100", epoxy equivalent 258g / eq.) 5 parts, active ester type curing agent ("HPC-8150-62T", active group equivalent 229g / eq., toluene solution with non-volatile content of 61.5% by mass) 43 parts, other hardeners (phenolic hardeners, DIC Corporation's "LA-3018-50P", hydroxyl equivalent 151 g / eq., 1-methoxy-2-propanol solution with non-volatile content of 50% by mass) 5 parts, (A) component low molecular weight polystyrene (Yasuhara Chemical Co., Ltd.'s "SX-100", Mw 2000) 10 parts, inorganic filler (spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573") (Admatechs Co., Ltd.'s "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m) 2 A resin varnish was obtained by mixing 135 parts of ethyl acetate / g), 0.5 parts of a curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ"), 10 parts of MEK, and 10 parts of cyclohexanone and dispersing the mixture uniformly using a high-speed rotating mixer.

[0203] [Example 2] In Example 1, 43 parts of the active ester curing agent ("HPC-8150-62T", active group equivalent 223 g / eq., toluene solution with non-volatile content of 61.5% by mass) was changed to 40 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq., toluene solution with non-volatile content of 65% by mass). A resin varnish was obtained in the same manner as in Example 1, except for the above points.

[0204] [Example 3] In Example 1, 43 parts of the active ester curing agent ("HPC-8150-62T", active group equivalent 223 g / eq., toluene solution with non-volatile content of 61.5% by mass) was changed to 43 parts of the active ester A (active group equivalent 238 g / eq., toluene solution with non-volatile content of 61.5% by mass) obtained in Synthesis Example 1. A resin varnish was obtained in the same manner as in Example 1 except for the above points.

[0205] [Example 4] In Example 1, 43 parts of an active ester-based curing agent (“HPC-8150-62T”, active group equivalent 223 g / eq., toluene solution with a non-volatile content of 61.5% by mass) was changed to 37 parts of active ester B (active group equivalent 214 g / eq., toluene solution with a non-volatile content of 70% by mass) obtained in Synthesis Example 2. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0206] [Example 5] In Example 1, 43 parts of an active ester-based curing agent (“HPC-8150-62T”, active group equivalent 223 g / eq., toluene solution with a non-volatile content of 61.5% by mass) was changed to 37 parts of an active ester-based curing agent (“PC1300-02-65MA” manufactured by Air Water, active group equivalent 199 g / eq., methyl amyl ketone solution with a non-volatile content of 65% by mass). A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0207] [Example 6] In Example 1, 2 parts of an MEK solution (non-volatile component 62% by mass) of a maleimide compound A (Mw / Mn = 1.81, t’’ = 1.47 (mainly 1, 2 or 3)) represented by the following formula (M) synthesized by the method described in Synthesis Example 1 of Japanese Patent Application Laid-Open No. 2020-500211 of the Japan Institute of Invention and Innovation was used. A resin varnish was obtained in the same manner as in Example 1 except for the above matters. [Chemical formula]

[0208] [Example 7] In Example 1, 2 parts of another thermosetting resin (maleimide resin (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd., toluene solution with a non-volatile content of 60% by mass)) was used. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0209] [Example 8] In Example 1, 2 parts of another thermosetting resin (maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., toluene / MEK mixed solution with a non-volatile content of 70% by mass)) were used. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0210] [Example 9] In Example 1, 2 parts of another thermosetting resin (maleimide resin ("BMI-689" manufactured by Degner Molecules)) were used. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0211] [Example 10] In Example 1, 2 parts of another thermosetting resin (acrylate resin ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.)) were used. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0212] [Example 11] In Example 1, 2 parts of another thermosetting resin (styryl resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Company, toluene solution with a non-volatile content of 65% by mass)) were used. A resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0213] [Example 13] In Example 1, instead of using 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as component (A), 10 parts of a styrene-(α-methylstyrene) copolymer ("FTR-0100" manufactured by Mitsui Chemicals, Inc.; Mw 1960) were added as component (A), and a resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0214] [Example 14] In Example 1, instead of using 10 parts of low molecular weight polystyrene ("SX-100" manufactured by Yasuhara Chemical Co., Ltd.) as component (A), 10 parts of a styrene-aromatic hydrocarbon copolymer ("FMR-0150" manufactured by Mitsui Chemicals, Inc.; Mw 2040) were added as component (A), and a resin varnish was obtained in the same manner as in Example 1 except for the above matters.

[0215] [Example 15] In Example 1, 10 parts of low molecular weight polystyrene (“SX-100” manufactured by Yasuhara Chemical Co., Ltd.) as component (A) was changed to 1 part, and an inorganic filler (spherical silica surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), “SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m 2 / g) 170 parts was changed to 145 parts, and a resin varnish was obtained in the same manner as in Example 1 except for the above changes.

[0216] [Example 16] In Example 1, 10 parts of low molecular weight polystyrene (“SX-100” manufactured by Yasuhara Chemical Co., Ltd.) as component (A) was changed to 15 parts, and an inorganic filler (spherical silica surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), “SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m 2 / g) 170 parts was changed to 185 parts, and a resin varnish was obtained in the same manner as in Example 1 except for the above changes.

[0217] [Comparative Example 1] In Example 1, a resin varnish was obtained in the same manner as in Example 1 except that 10 parts of low molecular weight polystyrene (“SX-100” manufactured by Yasuhara Chemical Co., Ltd.) as component (A) was not used.

[0218] [Comparative Example 2] In Example 1, instead of not using 10 parts of low molecular weight polystyrene (“SX-100” manufactured by Yasuhara Chemical Co., Ltd.) as component (A), (A′) another polystyrene (GPPS manufactured by PS Japan; Mw 190,000) was added, and a resin varnish was prepared in the same manner as in Example 1. However, since each component was not compatible and the varnish became gel-like, evaluation was impossible.

[0219] [Example 21] In Example 1, instead of 10 parts of low molecular weight polystyrene (“SX-100” manufactured by Yasuhara Chemical Co., Ltd.) as component (A), 3 parts of hydrogenated styrene (hydrogenated styrene or hydrogenated styrene-based polymer, Mw 2000, “SG-110” manufactured by Yasuhara Chemical Co., Ltd.) was added as component (A), and except that 170 parts of an inorganic filler (spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m 2 / g) was changed to 155 parts, a resin varnish was obtained in the same manner as in Example 1.

[0220] [Example 22] In Example 21, 43 parts of an active ester-based curing agent (“HPC-8150-62T”, active group equivalent 223 g / eq., toluene solution with non-volatile content of 61.5% by mass) was changed to 40 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent 223 g / eq., toluene solution with non-volatile content of 65% by mass). Except for the above matters, a resin varnish was obtained in the same manner as in Example 21.

[0221] [Example 23] In Example 21, 43 parts of an active ester-based curing agent (“HPC-8150-62T”, active group equivalent 223 g / eq., toluene solution with non-volatile content of 61.5% by mass) was changed to 43 parts of active ester A obtained in Synthesis Example 1 (active group equivalent 238 g / eq., toluene solution with non-volatile content of 61.5% by mass). Except for the above matters, a resin varnish was obtained in the same manner as in Example 21.

[0222] [Example 24] In Example 21, 43 parts of an active ester-based curing agent (“HPC-8150-62T”, active group equivalent 223 g / eq., toluene solution with non-volatile content of 61.5% by mass) was changed to 37 parts of active ester B obtained in Synthesis Example 2 (active group equivalent 214 g / eq., toluene solution with non-volatile content of 70% by mass). Except for the above matters, a resin varnish was obtained in the same manner as in Example 21.

[0223] [Example 25] In Example 21, 43 parts of an active ester-based curing agent (“HPC-8150-62T”, an active group equivalent of 223 g / eq., a toluene solution with a non-volatile content of 61.5% by mass) was changed to 37 parts of an active ester-based curing agent (“PC1300-02-65MA” manufactured by Air Water Inc., an active group equivalent of 199 g / eq., a methyl amyl ketone solution with a non-volatile content of 65% by mass). A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[0224] [Example 26] In Example 21, 2 parts of an MEK solution (non-volatile component: 62% by mass) of a maleimide compound A (Mw / Mn = 1.81, t’’ = 1.47 (mainly 1, 2, or 3)) represented by the following formula (M) synthesized by the method described in Synthesis Example 1 of Publication No. 2020-500211 of the Technical Report of the Japan Institute of Invention was used. A resin varnish was obtained in the same manner as in Example 21 except for the above matters. [Chemical formula]

[0225] [Example 27] In Example 21, 2 parts of another thermosetting resin (maleimide resin (“MIR-5000-60T” manufactured by Nippon Kayaku Co., Ltd., a toluene solution with a non-volatile content of 60% by mass)) was used. A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[0226] [Example 28] In Example 21, 2 parts of another thermosetting resin (maleimide resin (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., a toluene / MEK mixed solution with a non-volatile content of 70% by mass)) was used. A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[0227] [Example 29] In Example 21, 2 parts of another thermosetting resin (acrylate resin (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.)) was used. A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[0228] [Example 30] In Example 21, 2 parts of another thermosetting resin (styryl resin “OPE-2St-1200” manufactured by Mitsubishi Gas Chemical Company, toluene solution with a non-volatile content of 65% by mass) was used. A resin varnish was obtained in the same manner as in Example 21 except for the above matters.

[0229] <Test Example 1: Measurement of Dielectric Constant and Dissipation Factor> (1) Preparation of Resin Sheet A with a Resin Composition Layer Thickness of 40 μm As a support, a polyethylene terephthalate film (AL5 manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin varnishes obtained in the examples and comparative examples were uniformly coated so that the thickness of the resin composition layer after drying would be 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A including the support and the resin composition layer.

[0230] (2) Preparation of Cured Product The resin sheets A obtained in the examples and comparative examples were cured in an oven at 190°C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained. The cured product was cut into pieces with a length of 80 mm and a width of 2 mm to obtain a cured product for evaluation.

[0231] (3) Measurement of Dielectric Constant and Dissipation Factor For each cured product for evaluation, using “HP8362B” manufactured by Agilent Technologies, the values of dielectric constant and dissipation factor (Dk value and Df value) were measured at a measurement frequency of 5.8 GHz, measurement temperatures of 23°C and 90°C by the cavity resonance perturbation method. The measurement was carried out with two test pieces, and the average was calculated.

[0232] <Test Example 2: Evaluation of Crack Resistance after Desmear Treatment> (1) Preparation of Resin Sheet B with a Resin Composition Layer Thickness of 25 μm As a support, a polyethylene terephthalate film having a release layer (Lintec Corporation's "AL5", thickness 38 μm) was prepared. On the release layer of this support, the resin varnishes obtained in the examples and comparative examples were uniformly applied so that the thickness of the resin composition layer after drying would be 25 μm, and dried at 70°C to 80°C (average 75°C) for 2.5 minutes to obtain a resin sheet B including the support and the resin composition layer.

[0233] (2) Evaluation of Crack Resistance after Desmear Treatment On both sides of a core material (Hitachi Chemical Co., Ltd.'s "E705GR", thickness 400 μm) in which circular copper pads (copper thickness 35 μm) with a diameter of 350 μm were formed in a grid pattern at 400 μm intervals so that the residual copper rate would be 60% on the resin sheet B with a thickness of 25 μm prepared above, using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd.'s 2-stage build-up laminator "CVP700"), the resin composition layer was laminated on both sides of the inner layer substrate so as to be joined to the inner layer substrate. This lamination was carried out by reducing the pressure for 30 seconds to make the atmospheric pressure 13 hPa or less, and then crimping at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds. This was put into an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes. Further, the support layer was peeled off, and the obtained circuit board was immersed in Atotech Japan Co., Ltd.'s swelling dip security gant P, which is a swelling liquid, at 60°C for 10 minutes. Next, it was immersed in Atotech Japan Co., Ltd.'s concentrate compact P, which is a roughening liquid (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L), at 80°C for 30 minutes. Finally, it was immersed in Atotech Japan Co., Ltd.'s reduction solution security gant P, which is a neutralizing liquid, at 40°C for 5 minutes. 100 copper pad portions of the circuit board after the roughening treatment were observed to confirm the presence or absence of cracks in the resin composition layer. If the number of cracks was 10 or less, it was marked as "〇", and if it was more than 10, it was marked as "×".

[0234] <Test Example 3: Measurement of Glass Transition Temperature (Tg)> The resin sheet A obtained in Test Example 1 was cured in an oven at 190°C for 90 minutes, and then peeled from the support to obtain a cured film. This cured film was cut into samples for evaluation with a length of 20 mm and a width of 6 mm. For this evaluation sample, the glass transition temperature (Tg) was measured using a TMA apparatus (thermomechanical analyzer) manufactured by Rigaku Corporation at a heating rate of 5°C / min from 25°C to 250°C. The same test piece was measured twice, and the value of the second measurement was recorded.

[0235] The usage amounts (parts by mass) of components (A) to (G) including the volatile components of the resin compositions of the examples and comparative examples, and the measurement results of the test examples are shown in Table 1 below. In Table 1, the non-volatile content (mass %) of each component is represented in the "N.V." column.

[0236]

Table 1

[0237]

Table 2

[0238] From the above, it was found that by using a resin composition containing (A) a styrene-based and / or hydrogenated styrene-based polymer having a weight average molecular weight of 10,000 or less, (B) an epoxy resin, and (B) an active ester compound, a cured product excellent in crack resistance after desmear treatment can be obtained. It was also found that this cured product has a low dielectric tangent (Df) in both room temperature to normal temperature regions such as 23°C and high temperature environments such as 90°C, a low relative dielectric constant (Dk) in both room temperature to normal temperature regions and high temperature environments, and a high glass transition temperature.

Claims

1. A resin composition comprising: (A) a styrene-based and / or hydrogenated styrene-based polymer having a weight average molecular weight of 10,000 or less; (B) an epoxy resin; (C) an active ester compound; and (E) a radical polymerizable compound, (E) the radical polymerizable compound contains (E1) a maleimide compound, (E1) the maleimide compound includes (E1-2) a maleimide compound having a trimethylindane skeleton, The content of the component (A) is 1% by mass or more and 30% by mass or less, based on 100% by mass of the resin component in the resin composition; The content of the (B) component is 10% by mass or more and 60% by mass or less, based on 100% by mass of the resin component in the resin composition; A resin composition, wherein the content of the (C) component is 30% by mass or more and 70% by mass or less, based on 100% by mass of the resin components in the resin composition.

2. The resin composition according to claim 1, wherein the component (C) has a carbon-carbon double bond.

3. The resin composition according to claim 1 or 2, wherein the component (C) comprises an active ester compound containing a styryl group and a naphthalene structure.

4. The resin composition according to any one of claims 1 to 3, which is used for forming an interlayer insulating layer of a printed wiring board.

5. A cured product of the resin composition according to any one of claims 1 to 4.

6. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 4.

7. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 4 provided on the support.

8. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 4.

9. A semiconductor device comprising the printed wiring board according to claim 8.

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