Resin composition

Abstract

The object of the present invention is to provide a resin composition that can produce a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition temperature (Tg), and excellent copper adhesion. The solution of the present invention is a resin composition comprising (A) a maleimide compound having a bridged ring skeleton, and (B) an active ester compound.

Description

Technical Field

[0001] The present invention relates to a resin composition containing a maleimide compound and further to a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. Background Art

[0002] As the manufacturing technology of printed wiring board, the manufacturing method based on the stacking (buildup) mode of alternately stacked insulating layer and conductor layer is known. In the manufacturing method utilizing the stacking mode, generally speaking, the insulating layer is formed by curing the resin composition. In recent years, the dielectric constant and dielectric loss tangent of the demand insulating layer are further improved, and the copper adhesion is further improved. In addition, the insulating layer with high glass transition temperature is required.

[0003] Hitherto, maleimide compounds containing various non-aromatic ring skeletons are known (Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent document 1: Japanese Patent Application Publication No. 2019-203122. Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] An object of the present invention is to provide a resin composition capable of obtaining a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition temperature (Tg), and excellent copper adhesion.

[0009] Solutions for solving technical problems

[0010] In order to solve the problem of the present invention, the present inventors have conducted intensive studies and found that by using (A) a maleimide compound containing a bridged ring skeleton and (B) an active ester compound as components of a resin composition, it is unexpectedly possible to obtain a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition temperature (Tg), and excellent copper adhesion, thereby completing the present invention.

[0011] That is, the present invention includes the following contents;

[0012] [1] A resin composition comprising: (A) a maleimide compound having a bridged ring skeleton, and (B) an active ester compound;

[0013] [2] The resin composition according to [1] above, wherein the bridged ring in component (A) is a tricyclic bridged ring;

[0014] [3] The resin composition according to [2] above, wherein the bridge ring of the tricyclic ring system is a tricyclic [5.2.1.0 2,6 ]Decane ring;

[0015] [4] The resin composition according to any one of [1] to [3] above, wherein the number of maleimide groups in one molecule of component (A) is 2;

[0016] [5] The resin composition according to any one of [1] to [4] above, wherein the component (A) is a maleimide-terminated polyimide having a bridged ring skeleton;

[0017] [6] The resin composition according to any one of [1] to [5] above, wherein the component (A) further contains an aromatic tetracarboxylic acid diimide skeleton;

[0018] [7] The resin composition according to any one of [1] to [6] above, wherein the component (A) further contains a monocyclic non-aromatic ring skeleton;

[0019] [8] The resin composition according to any one of [1] to [7] above, wherein the component (A) is a bismaleimide compound represented by formula (A1).

[0020] [Chemical formula 1]

[0021]

[0022] [Where R 1 Each independently represents a substituent; X and Y 22 Each independently represents a single bond or a connecting group; Y 1 and Y 21 Each independently represents a single bond, an alkylene group or an alkenylene group; Z and Z 2 Each independently represents a monocyclic non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent; Z 1 Each independently represents a bridged ring optionally having a substituent; a each independently represents an integer of 0 to 2; b each independently represents 0 or 1; c, d and n2 each independently represent an integer of 0 or more than 1; n1 represents an integer of 1 or more; either m1 or m2 represents 1 and the other represents 0.]

[0023] [9] The resin composition according to any one of [1] to [8] above, wherein the weight average molecular weight of component (A) is 2,000 to 50,000;

[0024]

[10] The resin composition according to any one of [1] to [9] above, wherein the content of the component (A) is 3% to 30% by mass, based on 100% by mass of the nonvolatile component in the resin composition;

[0025]

[11] The resin composition according to any one of [1] to

[10] , further comprising (A') a radically polymerizable compound other than the component (A);

[0026]

[12] The resin composition according to any one of [1] to

[11] above, wherein the content of the component (A) is 50% by mass or more, based on 100% by mass of all radically polymerizable compounds in the resin composition;

[0027]

[13] The resin composition according to any one of [1] to

[12] above, wherein the content of the component (B) is 3% to 30% by mass, based on 100% by mass of the nonvolatile component in the resin composition;

[0028]

[14] The resin composition according to any one of [1] to

[13] above, wherein the mass ratio of component (A) to component (B) (component (A) / component (B)) is 0.5 to 3;

[0029]

[15] The resin composition according to any one of [1] to

[14] above, further comprising (C) an epoxy resin;

[0030]

[16] The resin composition according to any one of [1] to

[15] above, further comprising (D) an inorganic filler;

[0031]

[17] A cured product, which is a cured product of the resin composition described in any one of [1] to

[16] above;

[0032]

[18] A sheet-like laminated material comprising the resin composition described in any one of [1] to

[16] above;

[0033]

[19] A resin sheet comprising:

[0034] Support body, and

[0035] a resin composition layer formed from the resin composition described in any one of [1] to

[16] above and disposed on the support;

[0036]

[20] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition described in any one of [1] to

[16] above;

[0037]

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

[20] above.

[0038] Effects of the Invention

[0039] According to the resin composition of the present invention, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition temperature (Tg), and excellent copper adhesion can be obtained. DETAILED DESCRIPTION

[0040] Hereinafter, the present invention will be described in detail according to its preferred embodiments. 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 their equivalents.

[0041] <Resin composition>

[0042] The resin composition of the present invention comprises (A) a maleimide compound containing a bridged ring skeleton, and (B) an active ester compound. By using such a resin composition, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition temperature (Tg), and excellent copper adhesion can be obtained.

[0043] In the resin composition of the present invention, in addition to (A) a maleimide compound containing a bridged ring skeleton and (B) an active ester compound, an arbitrary component may be further included. As an arbitrary component, for example, (A') other free radical polymerizable compounds, (C) epoxy resins, (D) inorganic fillers, (E) curing accelerators, (F) other additives, and (G) organic solvents can be cited. Below, each component contained in the resin composition is described in detail.

[0044] <(A) Maleimide compound containing a bridged ring skeleton>

[0045] The resin composition of the present invention comprises (A) a maleimide compound containing a bridged ring skeleton. (A) The maleimide compound containing a bridged ring skeleton refers to an organic compound containing at least one bridged ring skeleton and at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) in the molecule. (A) The maleimide compound containing a bridged ring skeleton can be used alone or in combination of two or more in any proportion.

[0046] The bridge ring refers to a non-aromatic ring of two or more non-aromatic rings (preferably two to six rings, and particularly preferably three rings) that share two or more non-aromatic rings that share two or more (preferably three or more) atoms. The bridge ring may be a carbocyclic ring having carbon atoms as ring atoms, or a heterocyclic ring having heteroatoms selected from oxygen atoms, nitrogen atoms, and sulfur atoms as ring atoms in addition to carbon atoms. In one embodiment, it is preferably a carbocyclic ring. In one embodiment, the number of ring atoms of the bridge ring is preferably 6 to 15, more preferably 8 to 12, further preferably 9 to 11, and particularly preferably 10. The bridge ring may be a saturated ring or an unsaturated ring. In one embodiment, it is preferably a saturated ring. The bridge ring may be substituted by a substituent at a substitutable position.

[0047] The bridged ring is not particularly limited, and examples thereof include bicyclic bridged rings such as a bicyclo[2.2.1]heptane ring (i.e., a norbornane ring), a bicyclo[4.4.0]decane ring (i.e., a decalin ring), a bicyclo[5.3.0]decane ring, a bicyclo[4.3.0]nonane ring (i.e., a hexahydroindane ring), a bicyclo[3.2.1]octane ring, a bicyclo[5.4.0]undecane ring, a bicyclo[3.3.0]octane ring, and a bicyclo[3.3.1]nonane ring; and tricyclo[5.2.1.0 2,6 ] decane ring (i.e. tetrahydrodicyclopentadiene ring), tricyclic [3.3.1.1 3,7 ] decane ring (ie adamantane ring), tricyclic [6.2.1.0 2,7 In one embodiment, the bridged ring is preferably a bridged ring of a tricyclic ring system, and is particularly preferably a tricyclic [5.2.1.0 2,6 ]Decane ring.

[0048] In the present specification, the "substituent" is not particularly limited, and examples thereof include monovalent substituents such as alkyl, alkenyl, aryl, aryl-alkyl, alkyl-oxy, alkenyl-oxy, aryl-oxy, alkyl-carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl-carbonyl-oxy, and aryl-carbonyl-oxy. If substitutable, divalent substituents such as oxo (=O) may also be included.

[0049] Alkyl refers to a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. Alkyl is preferably an alkyl group having 1 to 14 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl, etc. Alkenyl refers to a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Alkenyl is preferably an alkenyl group having 2 to 14 carbon atoms. Examples of the alkenyl group include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, cyclohexenyl, etc. Aryl refers to a monovalent aromatic hydrocarbon group. Aryl is preferably an aryl group having 6 to 14 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0050] The number of bridged ring skeletons in one molecule of the maleimide compound (A) containing a bridged ring skeleton is preferably 2 or more, and the upper limit may be, for example, 20 or less, 10 or less. The number of maleimide groups in one molecule of the maleimide compound (A) containing a bridged ring skeleton is preferably 2 or more, particularly preferably 2.

[0051] In one embodiment, (A) the maleimide compound containing a bridged ring skeleton preferably also contains a monocyclic non-aromatic ring skeleton in the molecule. The monocyclic non-aromatic ring may be a carbocyclic ring or a heterocyclic ring, and in one embodiment, a carbocyclic ring is preferred. The number of ring atoms of the monocyclic non-aromatic ring is preferably 3 to 10 in one embodiment, more preferably 4 to 8, further preferably 5 or 6, and particularly preferably 6. The monocyclic non-aromatic ring may be a saturated ring or an unsaturated ring, and in one embodiment, a saturated ring is preferred. For the monocyclic non-aromatic ring, the substitutable position may be optionally substituted by a substituent.

[0052] As the monocyclic non-aromatic ring, for example, monocyclic alkane rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, etc.; monocyclic olefin rings such as cyclopentene ring, cyclohexene ring, cycloheptene ring, etc.; monocyclic non-aromatic heterocyclic rings such as pyrrolidine ring, tetrahydrofuran ring, dioxane ring, tetrahydropyran ring, etc. In one embodiment, the monocyclic non-aromatic ring is preferably a monocyclic alkane ring, particularly preferably a cyclohexane ring.

[0053] The number of monocyclic non-aromatic ring skeletons in one molecule of the maleimide compound (A) containing a bridged ring skeleton is preferably at least 2, and the upper limit may be, for example, 20 or less, 10 or less.

[0054] In one embodiment, the (A) bridged ring skeleton-containing maleimide compound preferably further contains an aromatic tetracarboxylic acid diimide skeleton in the molecule. Aromatic tetracarboxylic acid diimide is an imidized structure of aromatic tetracarboxylic acids (eg, pyromellitic acid, naphthalenetetracarboxylic acid, anthracenetetracarboxylic acid, diphthalic acid, etc.).

[0055] The aromatic tetracarboxylic acid diimide skeleton is preferably present in the molecule of the component (A) as a divalent group represented by the formula (X').

[0056] [Chemical formula 2]

[0057]

[0058] [Where R 1 Each independently represents a substituent (preferably an alkyl group); X each independently represents a single bond or a linking group (preferably a single bond, an alkylene group or -O-); Z' each independently represents a monocyclic non-aromatic ring optionally having a substituent, an aromatic ring optionally having a substituent, or a bridged ring optionally having a substituent (preferably an aromatic ring optionally having a substituent, and particularly preferably a benzene ring optionally having a substituent); a each independently represents an integer of 0 to 2 (preferably 0); b represents 0 or 1 (preferably 0); c represents an integer of 0 or more than 1 (preferably 0 or an integer of 1 to 5, and more preferably 0); * represents a bonding site. ]. It should be noted that, for each a unit and c unit, each unit may be the same or different.

[0059] In the present specification, examples of "linking groups" include alkylene, alkenylene, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, -OCO-, etc. In the present specification, "aromatic ring" includes not only monocyclic aromatic rings and condensed aromatic rings formed by condensing two or more monocyclic aromatic rings, but also condensed aromatic rings formed by condensing one or more monocyclic non-aromatic rings on one or more monocyclic aromatic rings, and examples include monocyclic aromatic rings (preferably 5- or 6-membered) such as benzene rings and pyridine rings, condensed aromatic rings (preferably 8-14-membered) such as indan rings, fluorene rings, and naphthalene rings. The aromatic ring may be a carbocyclic ring or a heterocyclic ring, and in one embodiment, a carbocyclic ring is preferred.

[0060] Alkylene refers to a straight-chain or branched divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms. Examples of the alkylene group include straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; ethylidene (-CH(CH3)-), propylidene (-CH(CH2CH3)-), isopropylidene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), diethylmethylene (-C(CH2CH3)2-), 2-methyltetramethylene, 2,3-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2-methylpentamethylene, 2,2-dimethylpentamethylene, 2,4-dimethylpentamethylene, 1,3,5-methylpentamethylene, 2-methylhexamethylene, 2,2-dimethylhexamethylene, 2,4-dimethylhexamethylene, 1,3,5-trimethylhexamethylene, 2,2,4-trimethylhexamethylene, 2,4,4-trimethylhexamethylene, etc. Branched alkylene groups, etc. Alkenylene refers to a straight chain or branched divalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Alkenylene is preferably an alkenylene having 2 to 14 carbon atoms. As an alkenylene group, for example, a group in which any carbon-carbon single bond in the group specifically exemplified as an alkylene group is replaced with a carbon-carbon double bond can be cited.

[0061] In the molecule of the maleimide compound (A) having a bridged ring skeleton, the number of aromatic tetracarboxylic acid diimide skeletons is preferably 2 or more, and the upper limit may be, for example, 40 or less, 20 or less, etc.

[0062] In one embodiment, (A) the maleimide compound containing a bridged ring skeleton is preferably a maleimide-terminated polyimide containing a bridged ring skeleton. Maleimide-terminated polyimide refers to a chain polyimide having a maleimide group at both ends (a chain polymer containing an imide structure in a repeating unit). It is known that maleimide-terminated polyimide can be obtained, for example, by imidizing a component containing a diamine compound, maleic anhydride and tetracarboxylic dianhydride.

[0063] The maleimide-terminated polyimide having a bridged ring skeleton is preferably a bismaleimide compound represented by the formula (A).

[0064] [Chemical formula 3]

[0065]

[0066] [Where n+1 A 1Each independently represents a divalent organic group (preferably an organic group containing a divalent ring (for example, a bridged ring, a monocyclic non-aromatic ring, or an aromatic ring)) formed by two or more (for example, 2 to 3000, 2 to 1000, 2 to 100, or 2 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (preferably carbon atoms); n A 2 Each independently represents, for example, a tetravalent organic group (preferably an organic group containing a tetravalent ring (for example, a bridged ring, a monocyclic non-aromatic ring, or an aromatic ring)) formed by two or more (for example, 2 to 3000, 2 to 1000, 2 to 100, or 2 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (preferably carbon atoms); n+1 A 1 , and n A 2 At least one of the units contains a bridged ring skeleton in the organic group; n represents an integer greater than 1 (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and particularly preferably an integer of 1 to 20). ]. It should be noted that for n units, each unit may be the same or different.

[0067] In one embodiment, preferably, n A 2 There is no bridged ring skeleton in the organic group, and n+1 A 1 At least one of A has a bridged ring skeleton in the organic group. In this preferred embodiment, A having a bridged ring skeleton 1 The number of A 1 The ratio of the total number (i.e., n+1) is preferably at least 0.1, more preferably at least 0.2, further preferably at least 0.3.

[0068] In one embodiment, n+1 A 1 Preferably, each is independently a divalent group represented by formula (Y1) or a divalent group represented by formula (Y2), and n+1 A 1 At least one of them is a divalent group represented by formula (Y1).

[0069] [Chemical formula 4]

[0070]

[0071] [In formula (Y1), Y 1 Each independently represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group, particularly preferably a methylene group); Z 1 represents a bridge ring optionally having a substituent (preferably a bridge ring of a tricyclic ring system, more preferably a tricyclic [5.2.1.0 2,6 ] decane ring (for example, at the 3 or 4 position and the 8 or 9 position with two Y 1 Combination); * indicates the binding site].

[0072] [Chemical formula 5]

[0073]

[0074] [In formula (Y2), Y 21 Each independently represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group, particularly preferably an octamethylene group); Y 22 Each independently represents a single bond or a linking group (preferably a single bond, an alkylene group or -O-); Z 2 Each independently represents a monocyclic non-aromatic ring optionally having a substituent, or an aromatic ring optionally having a substituent (preferably a monocyclic non-aromatic ring optionally having a substituent, more preferably a monocyclic alkane ring optionally having a substituent, and particularly preferably a cyclohexane ring optionally having a substituent); d represents an integer of 0 or more than 1 (preferably 0 or an integer of 1 to 5, more preferably 0); * represents a bonding site]. It should be noted that for the d units, each unit may be the same or different.

[0075] Specific examples of the divalent group represented by the formula (Y1) include divalent groups represented by the following formulae.

[0076] [Chemical formula 6]

[0077]

[0078] [Wherein, * represents the binding site].

[0079] Specific examples of the divalent group represented by formula (Y2) include divalent groups represented by the following formulae.

[0080] [Chemical formula 7]

[0081]

[0082] [Wherein, * represents the binding site].

[0083] In one embodiment, n A 2 Preferably, each independently represents a tetravalent group represented by formula (X).

[0084] [Chemical formula 8]

[0085]

[0086] [In the formula, Z each independently represents a monocyclic non-aromatic ring optionally having a substituent, or an aromatic ring optionally having a substituent (preferably an aromatic ring optionally having a substituent, particularly preferably a benzene ring optionally having a substituent); other symbols are the same as in formula (X')].

[0087] Specific examples of the tetravalent group represented by formula (X) include tetravalent groups represented by the following formulae.

[0088] [Chemical formula 9]

[0089]

[0090] [Wherein, * represents the binding site].

[0091] In one embodiment, the (A) maleimide compound having a bridged ring skeleton is preferably a bismaleimide compound represented by formula (A1) (the n1 unit and the n2 unit are bonded to each other).

[0092] [Chemical formula 10]

[0093]

[0094] [In formula (A1), n1 represents an integer greater than 1 (preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5); n2 represents an integer greater than 0 or 1 (preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5); either m1 or m2 represents 1, and the other represents 0 (preferably m2 represents 1 and m1 represents 0); other symbols are the same as in formulas (X'), (Y1), (Y2) and (X)].

[0095] (A) The maleimide compound containing a bridged ring skeleton is more preferably a bismaleimide compound represented by formula (A2),

[0096] [Chemical formula 11]

[0097]

[0098] [In formula (A2), each symbol is the same as in formula (X'), (Y1), (Y2), (X) and (A1)].

[0099] The maleimide compound (A) containing a bridged ring skeleton is preferably a bismaleimide compound represented by formula (A3),

[0100] [Chemical formula 12]

[0101]

[0102] [In formula (A3), R 2Each independently represents an alkyl group (preferably hexyl or octyl); y1 each independently represents an integer of 0 to 14 (preferably 0 to 3, particularly preferably 1); y2 each independently represents an integer of 0 to 14 (preferably 3 to 14, more preferably 6 to 10, particularly preferably 8); z represents an integer of 0 to 3 (preferably 1 or 2, particularly preferably 2); other symbols are the same as in formula (A1)].

[0103] (A) The maleimide compound having a bridged ring skeleton is particularly preferably a bismaleimide compound represented by formula (A4),

[0104] [Chemical formula 13]

[0105]

[0106] [In formula (A4), each symbol is the same as in formula (A1)]. It should be noted that in formulas (A1) to (A4), the order and configuration (arrangement) of the n1 unit and the n2 unit are not particularly limited, and include alternating copolymers, block copolymers, random copolymers, etc. In addition, for each n1 unit and n2 unit, each unit may be the same or different.

[0107] The weight average molecular weight (Mw) of the maleimide compound having a bridged ring skeleton (A) is preferably from 2000 to 50000, more preferably from 2500 to 40000, further preferably from 3000 to 20000. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

[0108] The functional group equivalent of the maleimide group of the maleimide compound having a bridged ring skeleton (A) is preferably from 500 g / eq. to 20,000 g / eq., more preferably from 1,000 g / eq. to 10,000 g / eq. The functional group equivalent of the maleimide group is the mass of the maleimide compound per 1 equivalent of the maleimide group.

[0109] Examples of commercially available products of the maleimide compound having a bridged ring skeleton (A) include "BMI-2500" (a bismaleimide compound of the above formula (A4)) manufactured by Designer Molecules.

[0110] The content of the maleimide compound of bridged ring skeleton contained in (A) in resin combination is not particularly limited, when the non-volatile component in resin combination is set to 100 mass %, preferably below 50 mass %, more preferably below 40 mass %, further preferably below 30 mass %, further more preferably below 20 mass %, especially preferably below 15 mass %. The lower limit of the content of the maleimide compound of bridged ring skeleton contained in (A) in resin combination is not particularly limited, when the non-volatile component in resin combination is set to 100 mass %, preferably more than 0.1 mass %, more preferably more than 1 mass %, further preferably more than 3 mass %, further more preferably more than 5 mass %, especially preferably more than 7 mass %.

[0111] <(A') Other radical polymerizable compounds>

[0112] The resin composition of the present invention may further contain (A') a radically polymerizable compound other than the component (A) as an optional component. The radically polymerizable compound (A') may be used alone or in any combination of two or more.

[0113] (A') The radical polymerizable compound may be, for example, a compound having a radical polymerizable unsaturated group. As the radical polymerizable unsaturated group, there is no particular limitation as long as free radical polymerization can be performed, and it is preferably an ethylenic unsaturated group having a carbon-carbon double bond at the end or inside, specifically, it may be an unsaturated aliphatic group such as allyl, 3-cyclohexenyl, etc.; an aromatic group containing an unsaturated aliphatic group such as p-vinylphenyl, m-vinylphenyl, styryl, etc.; an α,β-unsaturated carbonyl group such as acryloyl, methacryloyl, maleoyl, fumaroyl, etc. The radical polymerizable compound (A') preferably has one or more radical polymerizable unsaturated groups, and more preferably has two or more radical polymerizable unsaturated groups.

[0114] As (A') other radical polymerizable compounds, known radical polymerizable compounds can be widely used without particular limitation, and examples thereof include (A'-1) maleimide radical polymerizable compounds other than component (A), (A'-2) vinylphenyl radical polymerizable compounds, (A'-3) (meth)acrylic radical polymerizable compounds, etc.

[0115] <(A'-1) Maleimide-based radical polymerizable compound>

[0116] The (A'-1) maleimide-based free radical polymerizable compound is a compound other than the (A) component, and is an organic compound containing one or more (preferably two or more) maleimide groups in one molecule. The (A'-1) maleimide-based free radical polymerizable compound may be used alone or in combination of two or more in any proportion. The (A'-1) maleimide-based free radical polymerizable compound preferably comprises at least one maleimide compound selected from the group consisting of (A'-1-1) maleimide-terminated polyimide other than the (A) component, (A'-1-2) aromatic maleimide compounds, and (A'-1-3) aliphatic maleimide compounds.

[0117] <(A'-1-1) Maleimide-terminated polyimide>

[0118] (A'-1-1) Maleimide-terminated polyimide is a chain polyimide having maleimide groups at both ends without a bridged ring skeleton. (A'-1-1) Maleimide-terminated polyimide may be a component obtained by imidization reaction of components including a diamine compound, maleic anhydride, and tetracarboxylic dianhydride.

[0119] In one embodiment, the maleimide-terminated polyimide (A′-1-1) is, for example, a bismaleimide compound represented by formula (B).

[0120] [Chemical formula 14]

[0121]

[0122] [In formula (B), n+1 B 1 Each independently represents a divalent organic group (preferably an organic group containing a divalent ring (for example, a monocyclic non-aromatic ring or aromatic ring)) formed by two or more (for example, 2 to 3000, 2 to 1000, 2 to 100, or 2 to 50) skeletal atoms (preferably carbon atoms) selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms; n B 2 Each independently represents, for example, a tetravalent organic group (preferably an organic group containing a tetravalent ring (for example, a monocyclic non-aromatic ring or an aromatic ring, preferably an aromatic ring)) formed by two or more (for example, 2 to 3000, 2 to 1000, 2 to 100, or 2 to 50) skeletal atoms (preferably carbon atoms) selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms; n+1 B 1 , and n B 2The organic group does not contain a bridged ring skeleton; n represents an integer greater than 1 (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, particularly preferably an integer of 1 to 20)]. It should be noted that for n units, each unit may be the same or different.

[0123] In one embodiment, the maleimide-terminated polyimide (A′-1-1) is preferably a bismaleimide compound represented by the formula (B1).

[0124] [Chemical formula 15]

[0125]

[0126] [In formula (B1), Y 31 Each independently represents a single bond, an alkylene group or an alkenylene group; Y 32 Each independently represents a single bond or a connecting group; Z 3 Each independently represents a monocyclic non-aromatic ring optionally having a substituent, or an aromatic ring optionally having a substituent; e represents an integer of 0 or 1 or greater; and other symbols are the same as in formula (X) and formula (X')].

[0127] The weight average molecular weight (Mw) of the maleimide-terminated polyimide (A′-1-1) is preferably from 500 to 50,000, more preferably from 1,000 to 20,000.

[0128] The functional group equivalent of the maleimide group of the (A′-1-1) maleimide-terminated polyimide is preferably from 300 g / eq. to 20,000 g / eq., more preferably from 500 g / eq. to 10,000 g / eq.

[0129] As commercial products of (A′-1-1) maleimide-terminated polyimide, “BMI-1500”, “BMI-1700”, and “BMI-3000J” manufactured by Designer Molecules Co., Ltd. are mentioned, for example.

[0130] <(A'-1-2) Aromatic maleimide compound>

[0131] The (A'-1-2) aromatic maleimide compound is a maleimide compound that does not belong to the components (A) and (A'-1-1), and refers to a maleimide compound that contains one or more aromatic rings and two or more maleimide groups in one molecule. In one embodiment, the (A'-1-2) aromatic maleimide compound may be an addition-polymerized aromatic maleimide. The (A'-1-2) aromatic maleimide compound may be a maleimide compound having one aromatic ring, such as N,N'-1,3-phenylenedimaleimide and N,N'-1,4-phenylenedimaleimide, or a maleimide compound having two or more aromatic rings, preferably a maleimide compound having two or more aromatic rings.

[0132] In one embodiment, the (A′-1-2) aromatic maleimide compound is, for example, a maleimide compound represented by formula (C).

[0133] [Chemical formula 16]

[0134]

[0135] [In formula (C), R c Each independently represents a substituent; X c Each independently represents a single bond or a linking group (preferably a single bond or an alkylene group); Z c Each independently represents a monocyclic non-aromatic ring optionally having a substituent, or an aromatic ring optionally having a substituent (preferably an aromatic ring optionally having a substituent, and particularly preferably a benzene ring optionally having a substituent); s represents an integer greater than 1; t each independently represents an integer greater than 0 or 1; u each independently represents an integer from 0 to 2 (preferably 0)].

[0136] (A'-1-2) The aromatic maleimide compound is preferably a maleimide compound represented by formula (C1-1) to (C1-4),

[0137] [Chemical formula 17]

[0138]

[0139] [Where R c1 , R c2 and R c3 Each independently represents an alkyl group; X c1 and X c2Each independently represents a single bond or an alkylene group; s represents an integer greater than 1 (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, and further preferably an integer of 1 to 20); t' represents an integer of 1 to 5; u1, u2 and u3 each independently represent an integer of 0 to 2 (preferably 0)]. It should be noted that for the s unit, t unit, t' unit, u unit, u1 unit, u2 unit and u3 unit, each unit may be the same or different.

[0140] The functional group equivalent of the maleimide group of the aromatic maleimide compound (A′-1-2) is preferably from 50 to 2000 g / eq., more preferably from 100 to 1000 g / eq., further preferably from 150 to 700 g / eq., particularly preferably from 200 to 500 g / eq.

[0141] Commercially available products of the (A'-1-2) aromatic maleimide compound include, for example, "MIR-3000-70MT" (biphenyl aralkylphenol novolac type polymaleimide) manufactured by Nippon Kayaku Co., Ltd.; "BMI-50P" manufactured by KI-Chemical Co., Ltd.; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", and "BMI-5100" manufactured by Yamato Chemical Industries, Ltd.; "BMI-4,4'-BPE", "BMI-70", and "BMI-80" manufactured by KI-Chemical Co., Ltd.

[0142] <(A'-1-3) Aliphatic maleimide compound>

[0143] (A'-1-3) The aliphatic maleimide compound refers to a compound having a non-aromatic hydrocarbon (preferably having 2 to 50 carbon atoms) as a basic skeleton and having two or more (preferably 2) maleimide groups in one molecule.

[0144] In one embodiment, the (A′-1-3) aliphatic maleimide compound is, for example, a maleimide compound represented by formula (D).

[0145] [Chemical formula 18]

[0146]

[0147] [In formula (D), X d Each independently represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group or an alkenylene group); Z dEach independently represents a monocyclic non-aromatic ring optionally having a group selected from an alkyl group and an alkenyl group (preferably a monocyclic alkane ring or a monocyclic olefin ring optionally having a group selected from an alkyl group and an alkenyl group); x represents an integer greater than 0 or 1 (preferably an integer greater than 1, particularly preferably 1). It should be noted that for the x unit, each unit may be the same or different.

[0148] Specific examples of (A'-1-3) aliphatic maleimide compounds include: chain aliphatic bismaleimide compounds such as N,N'-ethylenebismaleimide, N,N'-tetramethylenebismaleimide, and N,N'-hexamethylenebismaleimide; alicyclic bismaleimide compounds such as 1-maleimide-3-maleimidemethyl-3,5,5-trimethylcyclohexane (IPBM), 1,1'-(cyclohexane-1,3-diylbismethylene)bis(1H-pyrrole-2,5-dione) (CBM), 1,1'-(4,4'-methylenebis(cyclohexane-4,1-diyl))bis(1H-pyrrole-2,5-dione) (MBCM); bismaleimide containing a dimer acid skeleton, etc.

[0149] The bismaleimide containing dimer acid skeleton refers to a bismaleimide compound in which the two terminal carboxyl groups (-COOH) of dimer acid are replaced by maleimide groups or maleimide methyl groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-ylmethyl). Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably unsaturated fatty acids having 11 to 22 carbon atoms, and particularly preferably unsaturated fatty acids having 18 carbon atoms), and its industrial manufacturing process has been almost standardized in the industry. For dimer acid, in particular, a substance with a dimer acid having 36 carbon atoms as the main component obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, which are cheap and easily available, can be easily obtained. In addition, for dimer acid, depending on the manufacturing method, the degree of purification, etc., it sometimes contains any amount of monomer acid, trimer acid, other polymerized fatty acids, etc. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, hydrogenated products whose unsaturation degree is reduced by further hydrogenation reaction are also included in dimer acids in the present specification.

[0150] The functional group equivalent of the maleimide group of the aliphatic maleimide compound (A′-1-3) is preferably from 50 g / eq. to 2000 g / eq., more preferably from 100 g / eq. to 1000 g / eq., further preferably from 200 g / eq. to 600 g / eq., particularly preferably from 300 g / eq. to 400 g / eq.

[0151] Examples of commercially available products of the aliphatic maleimide compound (A′-1-3) include “BMI-689”, “BMI-1500”, and “BMI-3000J” manufactured by Designer Molecules.

[0152] <(A'-2) Vinylphenyl radical polymerizable compound>

[0153] (A'-2) The vinylphenyl radical polymerizable compound is a radical polymerizable compound having a vinylphenyl group. The vinylphenyl radical polymerizable compound preferably has two or more vinylphenyl groups per molecule.

[0154] In one embodiment, the (A'-2) vinylphenyl-based free radical polymerizable compound is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and is particularly preferably a vinylbenzyl-modified polyphenylene ether having repeating units represented by formula (E-1) (the number of repeating units is preferably 2 to 300, more preferably 2 to 100) and vinylbenzyl groups (especially a vinylbenzyl-modified polyphenylene ether at both ends of the polyphenylene ether in which the hydrogen atoms of the hydroxyl groups at both ends of the polyphenylene ether are substituted with vinylbenzyl groups).

[0155] [Chemical formula 19]

[0156]

[0157] [In formula (E-1), R 11 , R 12 , R 13 and R 14 Each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group)].

[0158] In another embodiment, the (A′-2) vinylphenyl-based radically polymerizable compound is preferably a divinylbenzene polymer having a repeating unit represented by the formula (E-2) (the number of repeating units is preferably 2 to 200).

[0159] [Chemical formula 20]

[0160]

[0161] [In formula (E-2), R 15 , R 16 and R 17 Each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom). The divinylbenzene polymer may also be a copolymer having other styrene skeleton units such as styrene units and ethylstyrene units. When having other styrene skeleton units, the ratio of the repeating unit of formula (E-2) is preferably 5 to 70 mol% relative to all styrene skeleton units.

[0162] The number average molecular weight of the (A'-2) vinylphenyl radical polymerizable compound is preferably from 500 to 100000, more preferably from 700 to 80000. The vinyl functional group equivalent of the (A'-2) vinylphenyl radical polymerizable compound is preferably from 200 to 3000 g / eq., more preferably from 200 to 2000 g / eq.

[0163] Commercially available products of (A'-2) vinylphenyl-based free radical polymerizable compounds include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinyl benzyl-modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical Co., Ltd.; "ODV-XET-X03", "ODV-XET-X04", and "ODV-XET-X05" (divinylbenzene polymers) manufactured by Nippon Steel Chemicals Co., Ltd.

[0164] <(A'-3) (Meth)acrylic radical polymerizable compound>

[0165] (A'-3) (Meth) acrylic free radical polymerizable compound is a free radical polymerizable compound having an acryloyl group and / or a methacryloyl group. (A'-3) (Meth) acrylic free radical polymerizable compound preferably has two or more acryloyl groups and / or methacryloyl groups in one molecule. (A'-3) (Meth) acrylic free radical polymerizable compound is preferably a (meth) acrylic modified polyphenylene ether having an acryloyl group and / or a methacryloyl group and a polyphenylene ether skeleton, and is particularly preferably a (meth) acrylic modified polyphenylene ether having a repeating unit represented by formula (F) (the number of repeating units is preferably 2 to 300, more preferably 2 to 100) and an acryloyl group and / or a methacryloyl group (especially a two-terminal (meth) acrylic modified polyphenylene ether obtained by replacing the hydrogen atoms of the two terminal hydroxyl groups of the polyphenylene ether with acryloyl groups and / or methacryloyl groups).

[0166] [Chemical formula 21]

[0167]

[0168] [In formula (F), R 21 , R 22 , R 23 and R 24 Each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group)].

[0169] The number average molecular weight of the (A'-3) (meth) acrylic radical polymerizable compound is preferably from 500 to 10000, more preferably from 700 to 5000. The functional group equivalent of the acryloyl group and the methacryloyl group of the (A'-3) (meth) acrylic radical polymerizable compound is preferably from 200 g / eq. to 3000 g / eq., more preferably from 300 g / eq. to 2000 g / eq.

[0170] Examples of commercially available products of the (meth)acrylic radical polymerizable compound include “SA9000” and “SA9000-111” (methacrylic acid-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

[0171] The content of other radical polymerizable compounds (A') in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of other radical polymerizable compounds (A') in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it can be, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, etc.

[0172] When all the free radical polymerizable compounds in the resin composition (the total of component (A) and component (A')) are set to 100% by mass, the content of the maleimide compound (A) containing a bridged ring skeleton in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass or more.

[0173] <(B) Active ester compound>

[0174] The resin composition of the present invention contains (B) an active ester compound. (B) The active ester compound may be used alone or in combination of two or more in any proportion. In one embodiment, when the resin composition contains (C) an epoxy resin, or when the resin composition is mixed with (C) an epoxy resin, the (B) active ester compound may have a function of reacting with the (C) epoxy resin to crosslink the (C) epoxy resin.

[0175] As (B) active ester compound, it is generally preferred to use a compound having more than two highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc. The active ester compound is preferably a compound obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improved heat resistance, it is preferably an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound, and more preferably an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound. As the carboxylic acid compound, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. can be cited. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0176] Specifically, as (B) active ester compound, preferably 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 a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac, wherein 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 further preferred. As the dicyclopentadiene type active ester compound, preferably an active ester compound containing a dicyclopentadiene type diphenol structure. "Dicyclopentadiene type diphenol structure" means a divalent structural unit formed by phenylene-dicyclopentylene-phenylene.

[0177] Examples of commercially available active ester compounds (B) include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation); examples of commercially available active ester compounds containing a naphthalene structure include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-60T", and "EXB-8100L-65T". Examples of the active ester compounds include "EXB-50-62T", "EXB-9416-70BK", "HPC-8150-60T", and "HPC-8150-62T" (manufactured by DIC Corporation); examples of phosphorus-containing active ester compounds include "EXB9401" (manufactured by DIC Corporation); examples of active ester compounds that are acetylated products of linear phenolic resins include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds that are benzoylated products of linear phenolic resins include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds that contain styryl and naphthalene structures include "PC1300-02-65MA" (manufactured by AIR&WATER Corporation), etc.

[0178] The active ester group equivalent of the active ester compound (B) is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., further preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per 1 equivalent of active ester groups.

[0179] The content of the active ester compound (B) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less. The lower limit of the content of the active ester compound (B) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 7% by mass or more.

[0180] The mass ratio of the maleimide compound (A) containing a bridged ring skeleton to the active ester compound (B) in the resin composition (component (A) / component (B)) is preferably 0.1 or more, more preferably 0.5 or more, and particularly preferably 0.8 or more. The upper limit of the mass ratio of the maleimide compound (A) containing a bridged ring skeleton to the active ester compound (B) in the resin composition (component (A) / component (B)) is preferably 10 or less, more preferably 3 or less, and particularly preferably 1.5 or less.

[0181] <(C) Epoxy resin>

[0182] The resin composition of the present invention may contain (C) an epoxy resin as an optional component. (C) The epoxy resin is a curable resin having an epoxy group.

[0183] Examples of the epoxy resin (C) include bixylenol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butylcatechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, cresol novolac epoxy resins, and the like. The epoxy resins include, butadiene-based epoxy resins, cyclohexane-based epoxy resins, cyclohexanedimethanol-based epoxy resins, naphthylene ether-based epoxy resins, trimethylol-based epoxy resins, tetraphenylethane-based epoxy resins, isocyanurate-based epoxy resins, phenolphthalimidine-based epoxy resins, phenolphthalein-based epoxy resins, etc. The epoxy resin (C) may be used alone or in combination of two or more.

[0184] In the resin composition, an epoxy resin having two or more epoxy groups in one molecule is preferably included as the epoxy resin (C). The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more relative to 100% by mass of the non-volatile component of the epoxy resin (C).

[0185] The epoxy resin includes an epoxy resin that is liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). In the resin composition of the present invention, as the epoxy resin, only a liquid epoxy resin may be included, or only a solid epoxy resin may be included, or a liquid epoxy resin and a solid epoxy resin may be included in combination. 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.

[0186] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0187] As liquid epoxy resins, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure.

[0188] Specific examples of liquid epoxy resins include: "HP4032", "HP4032D", and "HP4032SS" (naphthalene-based epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "EPIKOTE "828EL" (bisphenol A type epoxy resin); "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" (glycidyloxy (Glycirol) 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 & Sumitomo Metal Chemical Corporation; Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX; "CELLOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resins with butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. These liquid epoxy resins can be used alone or in combination of two or more.

[0189] The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0190] As solid epoxy resins, preferred are biphenylol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, phenol benzopyrrolidone type epoxy resins, and phenolphthalein type epoxy resins.

[0191] Specific examples of solid epoxy resins 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 novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; D "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by IC Co., Ltd.; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel Chemicals; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemicals; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemicals; "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; Mitsubishi Chemical "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" (phenol benzopyrrolone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. These solid epoxy resins can be used alone or in combination of two or more.

[0192] When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin (C), 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, further preferably 1 or less, further preferably 0.5 or less, and particularly preferably 0.1 or less.

[0193] The epoxy equivalent of the epoxy resin (C) is preferably 50 g / eq. to 5000 g / eq., more preferably 60 g / eq. to 2000 g / eq., further preferably 70 g / eq. to 1000 g / eq., further preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.

[0194] (C) The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

[0195] The content of (C) epoxy resin in resin composition is not particularly limited, and when the non-volatile component in resin composition is set to 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit of the content of (C) epoxy resin in resin composition is not particularly limited, and when the non-volatile component in resin composition is set to 100% by mass, for example, more than 0% by mass, preferably more than 0.01% by mass, preferably more than 0.1% by mass, more preferably more than 1% by mass, further preferably more than 1% by mass, further more preferably more than 5% by mass, and particularly preferably more than 10% by mass.

[0196] The mass ratio of the maleimide compound (A) containing a bridged ring skeleton to the epoxy resin (C) in the resin composition (component (A) / component (C)) is preferably 0.1 or more, more preferably 0.3 or more, and particularly preferably 0.5 or more. The upper limit of the mass ratio of the maleimide compound (A) containing a bridged ring skeleton to the epoxy resin (C) in the resin composition (component (A) / component (C)) is preferably 10 or less, more preferably 3 or less, and particularly preferably 1 or less.

[0197] <(D) Inorganic fillers>

[0198] 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 the form of particles.

[0199] As the material of (D) inorganic filler, an inorganic compound is used. As the material of (D) inorganic filler, for example, silicon dioxide, aluminum oxide, 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, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc., can be cited. Among them, silicon dioxide is particularly preferred. As silicon dioxide, for example, amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silica, etc. can be cited. In addition, as silicon dioxide, spherical silicon dioxide is preferred. (D) The inorganic filler may be used alone or in combination of two or more in any ratio.

[0200] As commercially available products of (D) inorganic fillers, for example, there can be mentioned: "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE" and "YA010C" manufactured by Admatechs; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N" and "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Admatechs; "DAW-03" and "FB-105FD" manufactured by Denka, etc.

[0201] (D) The average particle size of the inorganic filler is not particularly limited, but it is preferably less than 10 μm, more preferably less than 5 μm, further preferably less than 2 μm, further preferably less than 1 μm, and particularly preferably less than 0.7 μm. (D) The lower limit of the average particle size of the inorganic filler is not particularly limited, but it is preferably more than 0.01 μm, more preferably more than 0.05 μm, further preferably more than 0.1 μm, and particularly preferably more than 0.2 μm. (D) The average particle size of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, a particle size distribution of an inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. The sample can be measured by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. For the measurement sample, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source used is blue and red. The volume-based particle size distribution of the inorganic filler is measured in a flow cell mode, and the average particle size is calculated as the median particle size based on the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" made by Horiba Manufacturing Co., Ltd. can be cited.

[0202] (D) The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, preferably 0.5m 2 / g or more, preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the inorganic filler (D) is not particularly limited, but is preferably 100 m 2 / g or less, preferably 70m 2 / g or less, preferably 50m 2 / g or less, particularly preferably 40m 2 The specific surface area of ​​the inorganic filler can be obtained by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area by the BET multipoint method.

[0203] The (D) inorganic filler material is preferably surface treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the (D) inorganic filler material can be improved. 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, 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Methacrylic silane coupling agents such as acyloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, Amino-based silane coupling agents such as 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; urea-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-isocyanatepropyltriethoxysilane; silane coupling agent; anhydride-based silane coupling agent such as 3-trimethoxysilylpropyl succinic anhydride; silane coupling agents such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane and other non-silane coupling-alkoxysilane compounds. In addition, the surface treatment agent may be used alone or in combination of two or more in any ratio.

[0204] Commercially available products of the surface treatment agent include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" ( "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-alkoxy silane compounds), etc.

[0205] From the viewpoint of improving the dispersibility of inorganic filler, the degree of surface treatment performed by surface treatment agent is preferably within the prescribed range. Specifically, for 100 mass % of inorganic filler, it is better to perform surface treatment by surface treatment agent of 0.2 mass % to 5 mass %, more preferably to perform surface treatment by surface treatment agent of 0.2 mass % to 3 mass %, and further preferably to perform surface treatment by surface treatment agent of 0.3 mass % to 2 mass %.

[0206] The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More than 0.1 mg / m 2 More than 0.2 mg / m 2 On the other hand, from the viewpoint of preventing the increase of the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, 1.0 mg / m2 Below, preferably 0.8mg / m 2 Below, preferably 0.5 mg / m 2 the following.

[0207] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, a carbon analyzer can be used to measure the amount of carbon per unit surface area of ​​the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0208] The content of (D) inorganic filler in resin combination is not particularly limited, and when the non-volatile component in resin combination is set to 100% by mass, it can be preferably below 90% by mass, more preferably below 80% by mass, further preferably below 75% by mass, and particularly preferably below 70% by mass. The lower limit of the content of (D) inorganic filler in resin combination is not particularly limited, and when the non-volatile component in resin combination is set to 100% by mass, it can be, for example, more than 0% by mass, more than 1% by mass, etc., it can be preferably more than 10% by mass, more preferably more than 30% by mass, further preferably more than 40% by mass, and particularly preferably more than 50% by mass.

[0209] The mass ratio of the maleimide compound (A) containing a bridged ring skeleton to the inorganic filler (D) in the resin composition (component (A) / component (D)) is preferably 0.01 or more, more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit of the mass ratio of the maleimide compound (A) containing a bridged ring skeleton to the inorganic filler (D) in the resin composition (component (A) / component (D)) is preferably 1 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less.

[0210] <(E) Curing accelerator>

[0211] The resin composition of the present invention may contain (E) a curing accelerator as an optional component.

[0212] Examples of the curing accelerator include phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, and amine curing accelerators. (E) The curing accelerator may be used alone or in combination of two or more.

[0213] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-toluene; Aromatic phosphonium salts such as triphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris(3-methylphenyl)ethylphosphonium tetraphenyl borate, tris(2-methoxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butylphosphine aliphatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine Aromatic phosphines such as tri(3,5-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(2-methoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl)phosphine, tri(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether can be used.

[0214] Examples of the urea curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1, Aromatic dimethylureas such as 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), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea], and the like.

[0215] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0216] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1') imidazole compounds such as 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, 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, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

[0217] As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemical Industries, Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0218] As metal curing accelerators, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II). As organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0219] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0220] As the amine-based curing accelerator, a commercially available product may be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd. and the like.

[0221] The content of (E) curing accelerator in resin combination is not particularly limited, but when the non-volatile component in resin combination is set to 100% by mass, it is preferably below 15% by mass, more preferably below 10% by mass, further preferably below 5% by mass, and particularly preferably below 3% by mass. The lower limit of the content of (E) curing accelerator in resin combination is not particularly limited, but when the non-volatile component in resin combination is set to 100% by mass, it can be, for example, more than 0% by mass, more than 0.001% by mass, more than 0.01% by mass, more than 0.1% by mass, more than 0.5% by mass, etc.

[0222] <(F) Other additives>

[0223] The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include free radical polymerization initiators such as peroxide-based free radical polymerization initiators and azo-based free radical polymerization initiators; epoxy curing agents other than active ester compounds such as phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, thiol-based curing agents, benzoxazine-based curing agents, cyanate-based curing agents, carbodiimide-based curing agents, and imidazole-based curing agents; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polyvinyl alcohol resins. Thermoplastic resins such as carbonate resin, polyetheretherketone resin, polyester resin, etc.; organic fillers such as rubber particles; organic metal 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; homogenizing agents such as silicone homogenizing agents and acrylic polymer homogenizing agents; thickeners such as Benton and montmorillonite; silicone defoamers, acrylic defoaming agents such as fluorochemical defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion enhancers 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 whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (such as phosphate compounds, phosphorus Flame retardants such as nitrile compounds, phosphinate compounds, red phosphorus), nitrogen flame retardants (such as melamine sulfate), halogen flame retardants, inorganic flame retardants (such as antimony trioxide), etc.; dispersants such as phosphate dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants, etc.; stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic anhydride stabilizers, etc. (F) Other additives can be used alone or in combination of two or more in any proportion. If you are a person skilled in the art, you can appropriately set the content of (F) other additives.

[0224] <(G) Organic solvent>

[0225] The resin composition of the present invention may contain any organic solvent as a volatile component in addition to the above-mentioned non-volatile components. As the (G) organic solvent, a known organic solvent may be used appropriately, and its type is not particularly limited. As the (G) organic solvent, for example: 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; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, carbitol acetate (ethyl diglycol Ether ester solvents such as 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. (G) Organic solvents can be used alone or in combination of two or more in any proportion.

[0226] In one embodiment, the content of the (G) organic solvent is not particularly limited, but when all the components in the resin composition are set to 100 mass%, for example, it can be 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, etc.

[0227] <Method for producing resin composition>

[0228] The resin composition of the present invention can be manufactured in the following manner, for example, in any preparation container, in any order and / or part or all of the same time, add (A) maleimide compounds containing bridged ring skeletons, (B) active ester compounds, (A') other free radical polymerizable compounds used as needed, (C) epoxy resins used as needed, (D) inorganic fillers used as needed, (E) curing accelerators used as needed, (F) other additives used as needed, and (G) organic solvents used as needed, and mix. In addition, in the process of adding each component and mixing, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or throughout. In addition, in the process of adding and mixing or after the process, for example, the resin composition can be stirred or vibrated using a stirring device or an oscillating device such as a mixer so that it is evenly dispersed. In addition, deaeration can be performed under low pressure conditions such as under vacuum while stirring or vibrating.

[0229] <Characteristics of resin composition>

[0230] The resin composition of the present invention comprises (A) a maleimide compound containing a bridged ring skeleton, and (B) an active ester compound. By using such a resin composition, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition temperature (Tg), and excellent copper adhesion can be obtained.

[0231] The cured product of the resin composition of the present invention may have a low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured under the conditions of 5.8 GHz and 23 ° C as in the following Test Example 1 may be preferably 0.020 or less, 0.010 or less, more preferably 0.009 or less, 0.008 or less, further preferably 0.007 or less, 0.006 or less, particularly preferably 0.005 or less, 0.004 or less.

[0232] The cured product of the resin composition of the present invention may have a low relative dielectric constant (Dk). Therefore, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition when measured under the conditions of 5.8 GHz and 23° C. as in the following Test Example 1 may preferably be 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, and particularly preferably 3.0 or less.

[0233] The cured product of the resin composition of the present invention may have a high glass transition temperature (Tg). Therefore, in one embodiment, the glass transition temperature (Tg) when measured as in the following Test Example 2 may preferably be 130°C or more, more preferably 140°C or more, further preferably 150°C or more, and particularly preferably 160°C or more.

[0234] The cured product of the resin composition of the present invention can have the feature that copper adhesion is excellent.Therefore, in one embodiment, the copper foil adhesion strength when being measured according to JIS C6481 as in the following test example 5 can be preferably more than 0.2kgf / cm, more preferably more than 0.3kgf / cm, further preferably more than 0.4kgf / cm, particularly preferably more than 0.5kgf / cm.For the upper limit, there is no particular restriction, for example, it can be set to below 10kgf / cm, etc.In addition, in one embodiment, the copper coating peeling strength calculated by the load when forming a copper-plated conductor layer on a cured product and peeling off the copper-plated conductor layer in a vertical direction as in the following test example 4 can be preferably more than 0.2kgf / cm, more preferably more than 0.3kgf / cm, further preferably more than 0.35kgf / cm, particularly preferably more than 0.4kgf / cm.For the upper limit, there is no particular restriction, for example, it can be set to below 10kgf / cm, etc.

[0235] In one embodiment, the cured product of the resin combination of the present invention can have the low such feature of the arithmetic mean roughness (Ra) of the surface after roughening treatment.Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the cured product surface after roughening treatment measured as in the following Test Example 3 can be preferably below 300nm, more preferably below 200nm, further preferably below 170nm, further more preferably below 150nm, especially preferably below 130nm.For lower limit, there is no particular restriction, for example, can be set to more than 1nm, more than 2nm, etc.

[0236] <Application of resin composition>

[0237] The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, especially a resin composition for forming an insulating layer. Specifically, it can be suitably used as: a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer), wherein the insulating layer is an insulating layer for forming a conductor layer (including a rewiring layer), and the conductor layer is formed on the insulating layer. In addition, in the printed wiring board described later, it can be suitably used as: a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be widely used in sheet-like laminated materials such as resin sheets, prepregs, solder resists, bottom filling materials, chip bonding materials, semiconductor sealing materials, filling resins (hole-filling resins), and parts embedding resins that require resin compositions.

[0238] Furthermore, 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 suitably used as a resin composition for a rewiring forming layer (resin composition for forming a rewiring forming layer) as an insulating layer for forming a rewiring layer, and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the sealing layer;

[0239] (1) a step of laminating a temporary fixing film on a substrate,

[0240] (2) a step of temporarily fixing the semiconductor chip on a temporary fixing film,

[0241] (3) a step of forming a sealing layer on a semiconductor chip,

[0242] (4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip,

[0243] (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled off, and

[0244] (6) A step of forming a rewiring layer as a conductive layer on the rewiring formation layer.

[0245] Furthermore, the resin composition of the present invention provides an insulating layer having good component embedding properties, and therefore can be preferably used when the printed wiring board is a component-embedded wiring board.

[0246] <Sheet-shaped laminated materials>

[0247] The resin composition of the present invention may be used by coating in a varnish state, but is usually preferably used in the form of a sheet-like laminate containing the resin composition in industrial terms.

[0248] As the sheet-like lamination material, a resin sheet or a prepreg as shown below is preferred.

[0249] 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 of the resin composition of the present invention.

[0250] From the viewpoint of thinning of 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 below 50 μm, more preferably below 40 μm. The lower limit of the thickness of the resin composition layer is not particularly limited, and can usually be set to above 5 μm, above 10 μm, etc.

[0251] Examples of the support include films formed of a plastic material, metal foil and release paper, and films formed of a plastic material and metal foil are preferred.

[0252] When a film formed of a plastic material is used as a support, the plastic material includes polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0253] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, preferably copper foil. The copper foil may be a foil made of a single metal of copper or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0254] The surface of the support that contacts the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

[0255] In addition, as a support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent for the release layer of a support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins can be cited. The support with a release layer can use a commercial product, for example, as a PET film having a release layer with an alkyd resin-based release agent as the main component, Lindeco's "SK-1", "AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Uniki (UNITIKA)'s "Unipeel" and the like can be cited.

[0256] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

[0257] In one embodiment, the resin sheet may further include an arbitrary layer as required. As the arbitrary layer, for example, a protective film selected according to the support body and disposed on the surface of the resin composition layer that is not bonded to the support body (i.e., the surface on the opposite side of the support body) can be cited. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, dust and the like can be prevented from adhering to the surface of the resin composition layer or from being damaged on the surface of the resin composition layer.

[0258] The resin sheet can be produced, for example, by directly applying a liquid resin composition to a support using a die coater or the like, or by preparing a resin varnish by dissolving the resin composition in an organic solvent and applying the resin varnish to a support using a die coater or the like, and then drying the varnish to form a resin composition layer.

[0259] Examples of the organic solvent include the same organic solvents as described as the component of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0260] Drying can be carried out by known methods such as heating and blowing hot air. There is no particular limitation on the drying conditions, and the drying is carried out in a manner such that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The drying conditions vary with the boiling point of the organic solvent in the resin composition or the resin varnish. For example, when a resin composition or a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition layer can be formed by drying at 50° C. to 150° C. for 3 minutes to 10 minutes.

[0261] 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.

[0262] In one embodiment, the prepreg is formed by impregnating the resin composition of the present invention into a sheet-like fiber base material.

[0263] The sheet-like fiber substrate used in the prepreg is not particularly limited, and glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, etc. can be used as materials commonly used as prepreg substrates. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. It is usually 10 μm or more.

[0264] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0265] The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0266] The sheet-like laminated material of the present invention can be suitably used to form an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

[0267] <Printed wiring board>

[0268] The printed wiring board of the present invention includes an insulating layer formed of a cured product obtained by curing the resin composition of the present invention.

[0269] Regarding the printed wiring board, for example, the above-mentioned resin sheet can be used to produce a method including the following steps (I) and (II);

[0270] (I) a step of laminating a resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate,

[0271] (II) A step of curing (for example, thermally curing) the resin composition layer to form an insulating layer.

[0272] The "inner substrate" used in step (I) refers to a member that becomes a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both sides of a substrate is sometimes referred to as an "inner circuit substrate". 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 so-called "inner substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

[0273] The lamination of the inner substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner substrate from the support body side. As a member for heat-pressing the resin sheet to the inner substrate (hereinafter also referred to as a "heat-pressing member"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) can be cited. It should be noted that it is better not to press the heat-pressing member directly to the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface unevenness of the inner substrate.

[0274] The lamination of the inner substrate and the resin sheet can be implemented by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably implemented under reduced pressure conditions with a pressure of 26.7hPa or less.

[0275] Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., and a batch vacuum pressure laminator.

[0276] After lamination, at normal pressure (atmospheric pressure), for example, the heat-pressed component can be pressed from the support side, thereby performing a smoothing treatment on the laminated resin sheet. The pressing conditions for the smoothing treatment can be set to the same conditions as the heat-pressed conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. It should be noted that the lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0277] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0278] In step (II), the resin composition layer is cured (eg, thermally cured) to form an insulating layer composed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions commonly used in forming an insulating layer of a printed wiring board can be used.

[0279] For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, and in one embodiment, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and further preferably 170° C. to 210° C. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.

[0280] The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, 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 further preferably 15 minutes to 100 minutes before the resin composition layer is thermally cured.

[0281] When manufacturing a printed wiring board, the step of (III) opening a hole in the insulating layer, the step of (IV) roughening the insulating layer, and the step of (V) forming a conductor layer can be further implemented. These steps (III) to (V) can be implemented according to various methods known to those skilled in the art that can be used in the manufacture of a printed wiring board. It should be noted that when the support is removed after step (II), the removal of the support can be implemented between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, as needed, the formation of the insulating layer and the conductor layer of steps (II) to (V) can be repeatedly implemented to form a multilayer wiring board.

[0282] In another embodiment, the printed wiring board of the present invention can be produced using the above-mentioned prepreg. The production method is basically the same as that in the case of using a resin sheet.

[0283] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as through holes and through holes in the insulating layer. Step (III) can be implemented using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used in forming the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the printed wiring board.

[0284] Step (IV) is a step of roughening the insulating layer. Usually, in step (IV), smear removal is also performed. The steps and conditions of the roughening treatment are not particularly limited, and the known steps and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially implementing a swelling treatment based on a swelling solution, a roughening treatment based on an oxidant, and a neutralization treatment based on a neutralizing solution.

[0285] There are no particular restrictions on the swelling liquid used in the roughening treatment, and examples include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, and more preferably sodium hydroxide solutions and potassium hydroxide solutions. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. There are no particular restrictions on the swelling treatment based on the swelling liquid, and for example, it can be carried out 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 better to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0286] As the oxidant used in the roughening treatment, there is no particular limitation, and an alkaline permanganate solution formed by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be cited. The roughening treatment based on an oxidant such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. As commercially available oxidants, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan can be cited.

[0287] The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securiganth P" manufactured by Atotech Japan Ltd.

[0288] The treatment with the neutralizing solution can be performed by immersing the treated surface after the roughening treatment with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. In view of operability, it is preferred to immerse the object after the roughening treatment with the oxidizing agent in the neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes.

[0289] In one embodiment, the root mean square roughness (Rq) of the insulating layer surface after roughening treatment is preferably less than 500nm, more preferably less than 400nm, and further preferably less than 300nm. There is no particular restriction on the lower limit, for example, it can be set to more than 1nm, more than 2nm, etc. The root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0290] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer can be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above metals (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be cited. Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of the formation of the conductor layer, 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 further preferred.

[0291] The conductor layer may be a single-layer structure, or a multilayer structure in which two or more single metal layers or alloy layers formed of different types of metals or alloys are stacked. When the conductor layer is 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 a nickel-chromium alloy.

[0292] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0293] In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated using a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. From the perspective of manufacturing simplicity, it is preferably formed using a semi-additive method. An example of forming a conductor layer using a semi-additive method is shown below.

[0294] 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 portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[0295] In other embodiments, the conductor layer can be formed using a metal foil. When a metal foil is used to form a conductor layer, step (V) is preferably implemented 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 can be implemented using a vacuum lamination method. The lamination conditions can be the same as those described for step (I). Next, step (II) is implemented to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer with a desired wiring pattern can be formed using previously known techniques such as a subtractive method and an improved semi-additive method.

[0296] The metal foil can be produced by a known method such as electrolysis or rolling. Commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Co., Ltd.

[0297] <Semiconductor devices>

[0298] 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 produced using the printed wiring board of the present invention.

[0299] Examples of the semiconductor device include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, and televisions) and vehicles (eg, motorcycles, cars, trains, ships, and airplanes).

[0300] Example

[0301] The present invention is specifically described below by way of examples. The present invention is not limited to these examples. It should be noted that, hereinafter, unless otherwise clearly stated, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass", respectively. The temperature condition is room temperature (25° C.) when no temperature is particularly specified.

[0302] <Example 1>

[0303] 10 parts of a maleimide compound containing a bridged ring skeleton ("BMI-2500" manufactured by Designer Molecules), 18.3 parts of an active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, a toluene solution having a solid content of 60% by mass), 18 parts of a naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd.), and spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd., with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m2) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with the following mixture:2 / g) and 1 part of an imidazole curing accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd., 1-benzyl-2-phenylimidazole) were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin composition.

[0304] <Example 2>

[0305] The resin composition was prepared in the same manner as in Example 1 except that the amount of the active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, a toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd.) was changed from 18 parts to 15 parts, and 5.7 parts of the biphenyl aralkyl phenol formaldehyde varnish type polymaleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with a solid content of 70%) was used.

[0306] <Example 3>

[0307] A MEK solution (non-volatile content 70% by mass) of a maleimide compound A (Mw / Mn=1.81, t″=1.47 (mainly 1, 2 or 3)) represented by the following formula (1) synthesized by the method described in Synthesis Example 1 of Japan Invention Association Publication No. 2020-500211 was prepared.

[0308] [Chemical formula 22]

[0309]

[0310] The resin composition was prepared in the same manner as in Example 1 except that the amount of the active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, a toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, the amount of the naphthol aralkyl epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd.) was changed from 18 parts to 15 parts, and 5.7 parts of maleimide compound A (a MEK solution with a solid content of 70%) was used.

[0311] <Example 4>

[0312] The resin composition was prepared in the same manner as in Example 1 except that the amount of the active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, a toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd.) was changed from 18 parts to 15 parts, and 6.2 parts of a terminal vinyl benzyl PPE compound ("OPE-2St-2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene mixed solution with a solid content of 65%) was used.

[0313] <Example 5>

[0314] A resin composition was prepared in the same manner as in Example 1 except that the amount of the active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, a toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd.) was changed from 18 parts to 15 parts, and 8 parts of a terminal methacrylic acid-modified PPE compound ("SA9000-111" manufactured by SABIC Innovative Plastics Co., Ltd., a solution with a solid content of 50% adjusted in toluene) was used.

[0315] <Example 6>

[0316] The resin composition was prepared in the same manner as in Example 1 except that the amount of the active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, a toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd.) was changed from 18 parts to 15 parts, and 6.2 parts of a divinylbenzene / styrene copolymer ("ODV-XET-X04" manufactured by Nippon Steel Chemical Materials Co., Ltd., a MEK / toluene mixed solution with a solid content of 65%) was used.

[0317] <Comparative Example 1>

[0318] A resin composition was prepared in the same manner as in Example 1 except that 10 parts of aliphatic maleimide ("BMI-689" manufactured by Designer Molecules) was used instead of 10 parts of the maleimide compound having a bridged ring skeleton ("BMI-2500" manufactured by Designer Molecules).

[0319] <Comparative Example 2>

[0320] A resin composition was prepared in the same manner as in Example 1, except that 14.3 parts of biphenyl aralkylphenol novolac type polymaleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with a solid content of 70%) was used instead of 10 parts of a maleimide compound containing a bridged ring skeleton ("BMI-2500" manufactured by Designer Molecules Co., Ltd.).

[0321] <Comparative Example 3>

[0322] A resin composition was prepared in the same manner as in Example 1, except that 10 parts of a maleimide compound containing a bridged ring skeleton ("BMI-2500" manufactured by Designer Molecules) was not used, the amount of an active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, a toluene solution having a solid content of 60% by mass) was changed from 18.3 parts to 26.7 parts, and the amount of a naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Materials Co., Ltd.) was changed from 18 parts to 23 parts.

[0323] <Comparative Example 4>

[0324] A resin composition was prepared in the same manner as in Example 1, except that 18.3 parts of an active ester compound (“HPC-8150-60T” manufactured by DIC Corporation, a toluene solution with a solid content of 60% by mass) was not used, the amount of spherical silica (“SO-C2” manufactured by Yaduma Corporation) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 60 parts to 51 parts, and 8.3 parts of a phenolic epoxy curing agent (“LA-7054” manufactured by DIC Corporation, a MEK solution with a solid content of 60%) was used.

[0325] <Test Example 1: Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)>

[0326] As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The resin composition obtained in the examples and comparative examples was evenly coated on the release layer of the support so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A comprising a support and a resin composition layer.

[0327] The obtained resin sheet A was cured in an oven at 190° C. for 90 minutes. The resin sheet A was taken out of the oven, and the support was peeled off from the resin sheet A, thereby obtaining a cured product of the resin composition layer. The cured product was cut into pieces with a length of 80 mm and a width of 2 mm to prepare a cured product B for evaluation.

[0328] The dielectric constant value (Dk value) and dielectric loss tangent value (Df value) of the evaluation cured product B were measured by the cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using “HP8362B” manufactured by Agilent Technologies. The measurement was performed on two test pieces, and the average value was calculated.

[0329] <Test Example 2: Measurement of glass transition temperature (Tg)>

[0330] The resin sheet A obtained in Test Example 1 was cured in an oven at 190°C for 90 minutes and then peeled off from the support to obtain a cured film. The cured film was cut into a length of 20 mm and a width of 6 mm as an evaluation sample. For the evaluation sample, a TMA device manufactured by Rigaku was used to increase the temperature from 25°C to 250°C at a heating rate of 5°C / min to measure the glass transition temperature (Tg). The same test piece was measured twice, and the second value was recorded.

[0331] <Test Example 3: Measurement of Arithmetic Mean Roughness (Ra)>

[0332] (1) Preparation of inner substrate

[0333] A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic) with an inner layer circuit formed on both sides was etched 1 μm with a microetchant ("CZ8101" manufactured by MEC) to roughen the copper surface.

[0334] (2) Lamination of resin sheet A

[0335] The resin sheet A obtained in Test Example 1 was laminated on both sides of the inner substrate using an intermittent vacuum pressurizing laminator (2-Stage Buildup Laminator, "CVP700", manufactured by Nikko-Materials) in such a way that the resin composition layer was in contact with the inner substrate. The lamination was performed by reducing the pressure for 30 seconds, adjusting the air pressure to 13 hPa or less, and then pressing at 120°C at a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100°C at a pressure of 0.5 MPa for 60 seconds.

[0336] (3) Thermal curing of resin composition layer

[0337] Then, the inner substrate laminated with the resin sheet A was placed in an oven at 130°C and heated for 30 minutes, and then moved to an oven at 170°C and heated for 30 minutes to thermally cure the resin composition layer to form an insulating layer. Then, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner substrate, and an insulating layer in this order.

[0338] (4) Roughening treatment

[0339] A desmear treatment as a roughening treatment was performed on the cured substrate A. As the desmear treatment, the following wet desmear treatment was performed.

[0340] (Wet decontamination treatment)

[0341] The cured substrate A was immersed in a swelling solution ("Swelling Dip Securiganth P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then immersed in an oxidant solution ("Concentrate Compact CP" manufactured by Atotech Japan, an aqueous solution of about 6% potassium permanganate and about 4% sodium hydroxide) at 80°C for 20 minutes. Then, it was immersed in a neutralizing solution ("Reduction Solution Securiganth P" manufactured by Atotech Japan, an aqueous solution of sulfuric acid) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

[0342] (5) Measurement of the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment

[0343] The arithmetic mean roughness (Ra) of the insulating layer surface of the cured substrate A after the roughening treatment was determined from the numerical values ​​obtained using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bruker Corporation) in VSI mode and a 50x lens with a measurement range of 121 μm×92 μm. The measurement was performed by calculating the average value of 10 points.

[0344] <Test Example 4: Measurement of peel strength of copper plating layer>

[0345] (1) Formation of copper-plated conductor layer

[0346] According to the semi-additive method, the roughened surface of the insulating layer of the cured substrate A obtained in Test Example 3 after the roughening treatment forms a conductor layer. That is, the roughened substrate is immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Then, it is heated at 150°C for 30 minutes, annealed, and then an anti-corrosion layer is formed, and patterning is performed by etching. Then, copper sulfate electroplating is performed to form a conductor layer with a thickness of 25μm, and annealing is performed at 190°C for 60 minutes. The resulting substrate is referred to as "evaluation substrate B".

[0347] (2) Determination of peel strength of copper-plated conductor layer

[0348] The peel strength between the insulating layer and the conductor layer was measured in accordance with Japanese Industrial Standard (JIS C6481). Specifically, a cut of 10 mm in width and 100 mm in length was made on the conductor layer of the evaluation substrate B, one end of the cut was peeled off and clamped with a clamp, and the load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min was measured at room temperature to obtain the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE Co., Ltd.) was used for the measurement.

[0349] <Test Example 5: Measurement of Copper Foil Adhesion Strength>

[0350] (1) Base treatment of copper foil

[0351] The shiny surface of "3EC-III" (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. was immersed in a microetchant ("CZ8101" manufactured by Mag Co., Ltd.) to roughen the copper surface (Ra value = 1 μm) and perform rust prevention treatment (CL8300). This copper foil is called CZ copper foil. Furthermore, it was heated in an oven at 130°C for 30 minutes.

[0352] (2) Copper foil lamination and insulation layer formation

[0353] An inner layer substrate laminated with resin sheet A was prepared in the same manner as in Test Example 1. Then, the supports on both sides were peeled off from the substrate to expose the resin composition layers on both sides. On these resin composition layers, the treated surface of the CZ copper foil of "3EC-III" was laminated under the same conditions as the lamination of the resin sheet A in Test Example 1. Then, the resin composition layer was cured under the curing conditions of 190°C and 90 minutes to form an insulating layer, thereby preparing a sample.

[0354] (3) Measurement of copper foil peeling strength (base adhesion)

[0355] The prepared sample was cut into small pieces of 150×30 mm. A cutter was used to cut a portion of 10 mm wide and 100 mm long on the copper foil portion of the small piece, and one end of the copper foil was peeled off and clamped with a clamp ("AC-50C-SL" manufactured by TSE Co., Ltd.), and the load [kgf / cm (N / cm)] when peeling off 35 mm in the vertical direction at a speed of 50 mm / min was measured at room temperature according to JIS C6481 using an Instron universal testing machine.

[0356] The amounts of nonvolatile components used in the resin compositions of Examples and Comparative Examples and the measurement results of Test Examples are shown in Table 1 below.

[0357] [Table 1]

[0358]

[0359] From the above, it can be seen that by using a resin composition containing (A) a maleimide compound containing a bridged ring skeleton and (B) an active ester compound, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition temperature (Tg), and excellent copper adhesion can be obtained.

Claims

1. A resin composition comprising: (A) a maleimide compound containing a bridged ring skeleton, (B) an active ester compound, (C) Epoxy resin, (D) Inorganic filling materials, and (A'-2) a vinylphenyl-based radical polymerizable compound and / or (A'-3) a (meth)acrylic-based radical polymerizable compound, Component (A) is a bismaleimide compound represented by formula (A4): In the formula, n1 represents an integer greater than 1, n2 represents an integer greater than 0 or 1, Component (B) is an active ester compound obtained from a carboxylic acid compound and a naphthol compound, When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 5% by mass to 30% by mass. When the nonvolatile components in the resin composition are set to 100% by mass, the content of the component (B) is 5% by mass to 30% by mass. When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 5% by mass to 30% by mass. When the nonvolatile components in the resin composition are set to 100 mass%, the content of the component (D) is 50 mass% to 80 mass%, and when the nonvolatile components in the resin composition are set to 100 mass%, the content of the component (A'-2) and / or the component (A'-3) is 0.1 mass% to 10 mass%.

2. The resin composition according to claim 1, wherein The weight average molecular weight of the component (A) is 2,000 to 50,000.

3. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 7% by mass or more.

4. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 15% by mass or less. 5 . The resin composition according to claim 1 , further comprising (A′) a radically polymerizable compound other than the component (A).

6. The resin composition according to claim 5, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the (A') component is 0.1 mass % or more.

7. The resin composition according to claim 5, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the (A') component is 2 mass % or more.

8. The resin composition according to claim 5, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A') is 50% by mass or less.

9. The resin composition according to claim 5, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A') is 10% by mass or less.

10. The resin composition according to claim 1, wherein When all the radical polymerizable compounds in the resin composition are taken as 100% by mass, the content of the component (A) is 10% by mass or more.

11. The resin composition according to claim 1, wherein When all the radical polymerizable compounds in the resin composition are taken as 100% by mass, the content of the component (A) is 50% by mass or more.

12. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 7% by mass or more.

13. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 15% by mass or less.

14. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.1 or more.

15. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 10 or less.

16. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.5 to 3.

17. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 0.8 or more.

18. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 1.5 or less.

19. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 10% by mass or more.

20. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 20% by mass or less.

21. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (C) (component (A) / component (C)) is 0.1 or more.

22. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (C) (component (A) / component (C)) is 0.5 or more.

23. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (C) (component (A) / component (C)) is 10 or less.

24. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (C) (component (A) / component (C)) is 1 or less.

25. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 70% by mass or less.

26. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (D) (component (A) / component (D)) is 0.01 or more.

27. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (D) (component (A) / component (D)) is 0.1 or more.

28. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (D) (component (A) / component (D)) is 1 or less.

29. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the component (D) (component (A) / component (D)) is 0.3 or less. 30 . A cured product, which is a cured product of the resin composition according to claim 1 .

31. A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 29.

32. A resin sheet comprising: Support body, and A resin composition layer formed from the resin composition according to any one of claims 1 to 29, provided on the support. 33 . A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 1 .

34. A semiconductor device comprising the printed wiring board according to claim 33.

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