Resin composition

Abstract

The present invention aims to provide a resin composition capable of producing a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df) and excellent peel strength of a plated conductor layer. The present invention provides a solution comprising: (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a maleimide compound having no aliphatic chain having 7 or more carbon atoms.

Description

Technical Field

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

[0002] As a manufacturing technology for printed wiring boards, a manufacturing method using a stacking (buildup) method of alternately overlapping insulating layers and conductor layers is known. In the manufacturing method using the stacking method, the insulating layer is generally formed by curing the resin composition. In recent years, it is expected that the dielectric constant and dielectric loss tangent of the insulating layer will be further improved, and the peel strength of the plated conductor layer will be further improved.

[0003] Various maleimide compounds are known so far (Patent Documents 1 to 3).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-203122

[0007] Patent Document 2: International Publication No. 2018 / 212116

[0008] Patent document 3: International Publication No. 2020 / 045489. Summary of the Invention

[0009] Technical problem to be solved by the invention

[0010] An 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) and excellent peel strength of a plated conductor layer.

[0011] Technical solutions used to solve technical problems

[0012] To solve the problems of the present invention, the present inventors conducted intensive studies and, as a result, discovered that by using a resin composition comprising (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a maleimide compound not having an aliphatic chain having 7 or more carbon atoms, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df) and excellent peel strength of the plated conductor layer can unexpectedly be obtained, thereby completing the present invention.

[0013] That is, the present invention includes the following contents;

[0014] [1] A resin composition comprising:

[0015] (A) an amine compound having a biphenyl skeleton,

[0016] (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and

[0017] (C) a maleimide compound that does not have an aliphatic chain having 7 or more carbon atoms;

[0018] [2] The resin composition according to [1] above, wherein the component (B) has: a maleimide group directly bonded (directly bound) to a carbon atom that does not constitute an aromatic ring;

[0019] [3] The resin composition according to [1] or [2] above, wherein the component (C) has: a maleimide group directly bonded to a carbon atom constituting an aromatic ring;

[0020] [4] The resin composition according to any one of [1] to [3] above, wherein the component (A) has a primary amino group;

[0021] [5] The resin composition according to any one of [1] to [4] above, wherein the component (A) has an amino group directly bonded to a carbon atom constituting an aromatic ring.

[0022] [6] The resin composition according to any one of [1] to [5] above, wherein

[0023] Component (A) comprises an amine compound having a repeating unit represented by formula (A1),

[0024] [Chemical Formula 1]

[0025]

[0026] In the formula, V and W each independently represent -C(R')2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, R each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent, and h, i and j each independently represent an integer from 0 to 2.

[0027] [7] The resin composition according to any one of [1] to [6] above, wherein the content of component (A) is 3% to 40% by mass, based on 100% by mass of the non-volatile component in the resin composition;

[0028] [8] The resin composition according to any one of [1] to [7] above, wherein the content of component (B) is 3% to 40% by mass, based on 100% by mass of the non-volatile component in the resin composition;

[0029] [9] The resin composition according to any one of [1] to [8] above, wherein the content of the component (C) is 3% to 40% by mass, based on 100% by mass of the non-volatile component in the resin composition;

[0030]

[10] The resin composition according to any one of [1] to [9] above, wherein the mass ratio of component (C) to component (B) (component (C) / component (B)) is 0.5 to 20;

[0031]

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

[10] above, wherein the mass ratio of component (A) to the total of component (B) and component (C) (component (A) / total of component (B) and component (C)) is 0.1 to 0.5;

[0032]

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

[11] above, further comprising (D) a radically polymerizable compound other than the components (B) and (C);

[0033]

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

[12] above, further comprising (E) an inorganic filler;

[0034]

[14] The resin composition according to

[13] above, wherein the content of the component (E) is 25% by mass or more, based on 100% by mass of the non-volatile component in the resin composition;

[0035]

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

[14] above, wherein a cured product of the resin composition has a dielectric loss tangent of 0.004 or less when measured at 5.8 GHz and 23°C.

[0036]

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

[15] above, wherein a cured product of the resin composition has a relative dielectric constant of 2.9 or less when measured at 5.8 GHz and 23°C.

[0037]

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

[16] above;

[0038]

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

[16] above;

[0039]

[19] A resin sheet comprising: a support; and a resin composition layer formed from the resin composition described in any one of [1] to

[16] above and provided on the support;

[0040]

[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;

[0041]

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

[20] above.

[0042] Effects of the Invention

[0043] According to the resin composition of the present invention, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df) and excellent peel strength of the plated conductor layer can be obtained. DETAILED DESCRIPTION

[0044] Hereinafter, the present invention will be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications without departing from the scope of the claims and their equivalents.

[0045] <Resin composition>

[0046] The resin composition of the present invention comprises (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a maleimide compound not having an aliphatic chain having 7 or more carbon atoms. By using such a resin composition, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df) and excellent peel strength of the plated conductor layer can be obtained.

[0047] In addition to (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a maleimide compound not having an aliphatic chain having 7 or more carbon atoms, the resin composition of the present invention may further contain arbitrary components. Examples of the arbitrary components include (D) an arbitrary radical polymerizable compound, (E) an inorganic filler, (F) a curing accelerator, (G) other additives, and (H) an organic solvent. The components contained in the resin composition are described in detail below.

[0048] <(A) Amine compound having a biphenyl skeleton>

[0049] The resin composition of the present invention contains (A) an amine compound having a biphenyl skeleton. One type of component (A) may be used alone, or two or more types may be used in any combination. In one embodiment, the amino group contained in component (A) may undergo addition reaction with component (B) and component (C) (and component (D) when component (D) is included). In one embodiment, component (A) preferably has two or more amino groups in one molecule, and more preferably has three or more amino groups in one molecule. In component (A), as an amino group, any of primary, secondary and tertiary amino groups may be present, and in one embodiment, a primary amino group is preferably present. In one embodiment, in component (A), as an amino group, an amino group directly bonded to a carbon atom constituting an aromatic ring (aromatic amino group) is preferably present, and an aromatic primary amino group is more preferably present, and it is particularly preferred that the amino group contained in component (A) is only an aromatic primary amino group.

[0050] In one embodiment, the component (A) preferably contains an amine compound having a repeating unit represented by the formula (A1).

[0051] [Chemical Formula 2]

[0052]

[0053] [In the formula, V and W each independently represent -C(R')2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO- (preferably -C(R')2-), R each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom), and h, i and j each independently represent an integer from 0 to 2 (preferably 0)].

[0054] It should be noted that, regarding the h unit, the i unit, and the j unit, each unit may be the same or different.

[0055] In the present specification, the substituent is not particularly limited, and examples thereof include monovalent substituents such as alkyl, alkenyl, aryl, alkyl-aryl (aryl substituted with one or more alkyl groups), aryl-aryl (aryl substituted with one or more aryl groups), aryl-alkyl (alkyl substituted with one or more aryl groups), 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. As long as the substitutable group is possible, a divalent substituent such as oxo (=O) may also be included.

[0056] "Alkyl" refers to a linear, branched, and / or cyclic monovalent saturated hydrocarbon group. The alkyl group is not particularly specified, but is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 or 4 to 10 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, and cyclopentylmethyl. Alkenyl refers to a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group is not particularly specified, but is preferably an alkenyl group having 2 to 14 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, and even more preferably an alkenyl group having 2 to 6 or 4 to 10 carbon atoms. Examples of alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and cyclohexenyl. An aryl group refers to a monovalent aromatic hydrocarbon group. An aryl group is preferably an aryl group having 6 to 14 carbon atoms. Examples of aryl groups include phenyl, 1-naphthyl, and 2-naphthyl.

[0057] The weight average molecular weight (Mw) of the component (A) is preferably from 300 to 4000, more preferably from 300 to 3000, further preferably from 300 to 2000. The weight average molecular weight of the component (A) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0058] The functional group equivalent of the amino group of the component (A) is preferably from 100 g / eq. to 1000 g / eq., more preferably from 100 g / eq. to 500 g / eq. The functional group equivalent of the amino group of the component (A) is the mass of the component (A) per 1 equivalent of the amino group.

[0059] Specific examples of the component (A) include amine compounds having a repeating unit represented by the formula (A2).

[0060] [Chemical Formula 3]

[0061]

[0062] As a commercial item of (A) component, "BAN" (amine compound of the said formula (A2)) etc. are mentioned, for example by Nippon Kayaku Co., Ltd.

[0063] The content of (A) component in resin combination is not particularly limited. When the non-volatile component in resin combination is set to 100 mass %, it is preferably below 60 mass %, more preferably below 50 mass %, further more preferably below 40 mass %, further more preferably below 30 mass %, and particularly preferably below 25 mass %. The lower limit of the content of (A) component in resin combination is not particularly limited. When the non-volatile component in resin combination is set to 100 mass %, it is preferably more than 0.1 mass %, more preferably more than 1 mass %, further more preferably more than 3 mass %, further more preferably more than 5 mass %, and particularly preferably more than 7 mass %.

[0064] <(B) Maleimide compound having an aliphatic chain having 7 or more carbon atoms>

[0065] The resin composition of the present invention contains (B) a maleimide compound having a fatty chain with 7 or more carbon atoms. One type of component (B) may be used alone, or two or more types may be used in any combination. A maleimide compound refers to an organic compound containing at least one (preferably two or more) maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) in one molecule. In one embodiment, component (B) preferably has a maleimide group directly bonded to a carbon atom that does not constitute an aromatic ring, and it is particularly preferred that the maleimide group contained in component (B) is only a maleimide group directly bonded to a carbon atom that does not constitute an aromatic ring.

[0066] The fatty chain refers to a fatty chain in which backbone atoms are linked via single bonds, double bonds, or triple bonds, preferably a fatty chain in which backbone atoms are linked via single bonds or double bonds, and particularly preferably a fatty chain in which backbone atoms are linked only via single bonds. In addition, the fatty chain may have branches, but they do not constitute part or all of the ring structure.

[0067] The fatty chain may be an aliphatic carbon chain having only carbon atoms as backbone atoms (e.g., an alkylene chain, an alkenylene chain, etc.), or a heteroatom-containing fatty chain having heteroatoms selected from oxygen atoms, nitrogen atoms, and sulfur atoms as backbone atoms in addition to carbon atoms (e.g., a polyalkylene oxide chain, a polyalkylene imine chain, etc.). In one embodiment, an aliphatic carbon chain having only carbon atoms as backbone atoms is preferably used. The upper limit of the number of carbon atoms in the backbone atoms of the fatty chain is not particularly limited, and may be, for example, less than 3000, less than 1000, less than 100, less than 50, etc. A fatty chain having more than 7 carbon atoms preferably has a fatty chain main chain having more than 7 carbon atoms.

[0068] In one embodiment, the maleimide compound of the component (B) preferably includes a maleimide compound represented by formula (B1).

[0069] [Chemical Formula 4]

[0070]

[0071] [Where A 1 Each independently represents a divalent organic group having an aliphatic chain having 7 or more carbon atoms, A 2 Each independently represents a divalent organic group having no aliphatic chain having 7 or more carbon atoms, 1 Each independently represents a tetravalent organic group having an aromatic ring and / or a non-aromatic ring, n1 and n2 represent an integer of 0 or greater (preferably 0 or an integer of 1 to 100), one of m1 and m2 represents 1 and the other represents 0, and the total of n1 and m1 is 1 or greater. It should be noted that the order and respective configurations of the n1 unit and the n2 unit are arbitrary, including alternating copolymers, block copolymers, random copolymers, etc. In addition, for each of the n1 unit and the n2 unit, each unit may be the same or different.

[0072] The aromatic ring refers to a ring that follows Hückel's rule in which the number of electrons contained in the π electron system on the ring is 4n+2 (n is a natural number). The aromatic ring can be a carbocyclic ring with carbon atoms as ring atoms or a heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in addition to carbon atoms as ring atoms. In one embodiment, a carbocyclic ring is preferably used. The aromatic ring includes not only a monocyclic aromatic ring and a condensed ring obtained by condensing two or more monocyclic aromatic rings, but also a condensed ring obtained by condensing one or more monocyclic non-aromatic rings on one or more monocyclic aromatic rings. As specific examples of aromatic rings, benzene rings, naphthalene rings, anthracene rings, indane rings, fluorene rings, tetralin rings, etc. can be cited.

[0073] A non-aromatic ring refers to a ring other than an aromatic ring. The non-aromatic ring may be a carbocyclic ring or a heterocyclic ring, and in one embodiment, a carbocyclic ring is preferred. The non-aromatic ring may be a saturated ring or an unsaturated ring, and in one embodiment, a saturated ring is preferred. Non-aromatic rings include monocyclic non-aromatic rings such as cycloalkane rings and cycloalkene rings, and fused non-aromatic rings obtained by condensing two or more monocyclic non-aromatic rings such as bridged hydrocarbon rings. A cycloalkane ring is a monocyclic aliphatic saturated hydrocarbon ring, and examples thereof include cycloalkane rings having 3 to 8 carbon atoms, such as cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, and cyclooctane rings. A cycloalkene ring is a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond, and examples thereof include cycloalkene rings having 4 to 8 carbon atoms, such as cyclobutene rings, cyclopentene rings, cyclohexene rings, cycloheptene rings, cyclooctene rings, cyclopentadiene rings, and cyclohexadiene rings. The bridged hydrocarbon ring is a non-aromatic ring formed by two or more rings sharing two or more atoms, and examples thereof include bridged hydrocarbon rings having 8 to 15 carbon atoms, such as a norbornane ring, a decalin ring, an adamantane ring, and a tetrahydrodicyclopentadiene ring.

[0074] When n1 is at least 1, the ratio of n1 to n2 (n2 / n1) is preferably at most 5.0, more preferably at most 2.0, further preferably at most 1.5, particularly preferably at most 1.2.

[0075] A 1 Each independently represents a divalent organic group having an aliphatic chain with 7 or more carbon atoms. 1 The backbone atoms of the "divalent organic group" represented are, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms. The number of backbone atoms is not particularly limited and may be, for example, 3000 or less, 1000 or less, 100 or less, 50 or less, etc.

[0076] In one embodiment, A 1 Each of the diamine groups is preferably a divalent group formed by removing two amino groups from a dimer diamine. A dimer diamine is a compound obtained by replacing the two terminal carboxyl groups (-COOH) of a dimer acid with amino groups or aminomethyl groups, and has an aliphatic carbon chain having 7 or more carbon atoms. For example, a dimer acid is a dimer of an unsaturated fatty acid (preferably an unsaturated fatty acid having 11 to 22 carbon atoms, particularly preferably an unsaturated fatty acid having 18 carbon atoms, such as oleic acid or linoleic acid) or a hydrogenated product thereof.

[0077] In another embodiment, A 1 Each independently is preferably a divalent non-aromatic hydrocarbon group having an aliphatic carbon chain having at least 7 carbon atoms.

[0078] A 1 More preferably, each independently is a divalent group represented by formula (b1),

[0079] [Chemical Formula 5]

[0080]

[0081] [Where Y 1 Each independently represents a linear or branched (preferably linear) alkylene group having 7 or more atoms (preferably the number of atoms in the alkylene main chain), or a linear or branched (preferably linear) alkenylene group having 7 or more atoms (preferably the number of atoms in the alkenylene main chain), preferably a linear or branched (preferably linear) alkylene group having 7 or more carbon atoms, and ring Z y1 represents a cycloalkane ring which may have a group selected from an alkyl group and an alkenyl group, or a cycloolefin ring which may have a group selected from an alkyl group and an alkenyl group, preferably a cyclohexane ring which may have an alkyl group, d represents 0 or 1 (preferably 1), and * represents a bonding site].

[0082] An alkylene group refers to a divalent saturated hydrocarbon group. The number of carbon atoms of a linear or branched alkylene group having 7 or more carbon atoms is, for example, 7 to 200, preferably 7 to 100, and more preferably 7 to 50. An alkenylene group refers to a divalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The number of carbon atoms of a linear or branched alkenylene group having 7 or more carbon atoms is, for example, 7 to 200, preferably 7 to 100, and more preferably 7 to 50.

[0083] Specific examples of the divalent group represented by formula (b1) include divalent groups represented by the following formulae.

[0084] [Chemical Formula 6]

[0085]

[0086] [Wherein, * represents the binding site].

[0087] A 2 Each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms (that is, when having an aliphatic chain, the aliphatic chain having the most carbon atoms among these aliphatic chains has 6 or less carbon atoms). 2 The backbone atoms of the "divalent organic group" represented by A are selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms, and the number of backbone atoms is not particularly limited, and may be, for example, 5 to 3000, 5 to 1000, 5 to 100, or 5 to 50. 2 For example, it is a divalent group obtained by removing two amino groups from a diamine compound having no aliphatic chain having 7 or more carbon atoms, which is generally used as a raw material for polyimide, and is not particularly limited.

[0088] A 2 Each independently preferably is a divalent organic group that does not have an aliphatic chain having more than 7 carbon atoms and has an aromatic ring and / or a non-aromatic ring (that is, in the case of having an aliphatic chain, the aliphatic chain with the largest number of carbon atoms among these aliphatic chains has a carbon atom number of 6 or less and has an aromatic ring and / or a non-aromatic ring), and is more preferably a divalent group represented by formula (b2).

[0089] [Chemical Formula 7]

[0090]

[0091] [Where Y 21 Each independently represents a single bond, or -C(R x )2-(preferably -C(R x )2-), Y 22 Each independently represents a single bond, -C(R y)2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO- (preferably -C(R y )2- or -O-), R x and R y Each independently represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group (preferably a hydrogen atom), and ring Z y2

[0065] Each independently represents a non-aromatic ring which may have a group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, or an aromatic ring which may have a group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, e represents an integer of 0 or greater (preferably 0 or an integer of 1 to 5), and * represents a bonding site. It should be noted that the e unit may be the same or different for each unit.

[0092] Specific examples of the divalent group represented by formula (b2) include divalent groups represented by the following formulae.

[0093] [Chemical Formula 8]

[0094]

[0095] [Wherein, * represents the binding site].

[0096] B 1 Each independently represents a tetravalent organic group having an aromatic ring and / or a non-aromatic ring. 1 The backbone atoms of the "quaternary organic group" represented by B are selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms, and the number of backbone atoms is not particularly limited, and may be, for example, 5 to 3000, 5 to 1000, 5 to 100, or 5 to 50. 1 For example, it is a tetravalent group obtained by removing two acid anhydride groups (—CO—O—CO—) from tetracarboxylic anhydride having an aromatic ring and / or a non-aromatic ring, which is generally used as a raw material for polyimide, and is not particularly limited.

[0097] B 1 Each independently preferably is a tetravalent organic group that does not have an aliphatic chain having more than 7 carbon atoms and has an aromatic ring and / or a non-aromatic ring (that is, in the case of having an aliphatic chain, the aliphatic chain with the largest number of carbon atoms among these aliphatic chains has a carbon atom number of 6 or less and has an aromatic ring and / or a non-aromatic ring), and is more preferably a tetravalent group represented by formula (b3).

[0098] [Chemical Formula 9]

[0099]

[0100] [Where R 1 Each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, X 1 Each independently represents a single bond, -C(Rz )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO- (preferably -C(R z )2- or -O-), R z Each independently represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group (preferably a hydrogen atom), and ring Z x1

[0065] Each independently represents a non-aromatic ring which may have a group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, or an aromatic ring which may have a group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, a each independently represents an integer of 0 to 2 (preferably 0), b represents 0 or 1, c represents an integer of 0 or more than 1 (preferably 0 or an integer of 1 to 5), and * represents a bonding site. It should be noted that, for each of the a unit and the c unit, the units may be the same or different.

[0101] Specific examples of the tetravalent group represented by formula (b3) include tetravalent groups represented by the following formulae.

[0102] [Chemical Formula 10]

[0103]

[0104] [Wherein, * represents the binding site].

[0105] In one embodiment, the maleimide compound of the component (B) is more preferably a compound represented by formula (B2) (where n1 unit and n2 unit are bonded to each other).

[0106] [Chemical Formula 11]

[0107]

[0108] [In the formula, each symbol is the same as in formulas (B1), (b1), (b2) and (b3)].

[0109] The maleimide compound of the component (B) is more preferably a compound represented by formula (B3) (where n1 unit and n2 unit are connected by a bond),

[0110] [Chemical Formula 12]

[0111]

[0112] [In the formula, each symbol is the same as in formulas (B1), (b2) and (b3)].

[0113] Specific examples of the component (B) include maleimide compounds represented by formulae (B4-1) to (B4-5).

[0114] [Chemical Formula 13]

[0115]

[0116] [In the formula, n1′ and n2′ each independently represent an integer of 1 to 20, preferably an integer of 1 to 10.] The order and arrangement of the n1′ unit and the n2′ unit are arbitrary, including alternating copolymers, block copolymers, random copolymers, and the like.

[0117] The weight average molecular weight (Mw) of the component (B) is not particularly limited, but is preferably from 200 to 50,000, more preferably from 300 to 40,000, further preferably from 400 to 20,000. The weight average molecular weight of the component (B) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0118] As commercially available products of the component (B), for example, "BMI-689", "BMI-1500", "BMI-1700", "BMI-3000J", and "BMI-2500" manufactured by Designer Molecules Co., Ltd. may be mentioned.

[0119] The content of (B) component 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 more preferably below 30 mass %, further more preferably below 25 mass %, especially preferably below 20 mass %. The lower limit of the content of (B) component in resin combination is not particularly limited, when the non-volatile component in resin combination is set to 100 mass %, preferably more than 1 mass %, more preferably more than 3 mass %, further more preferably more than 5 mass %, further more preferably more than 10 mass %, especially preferably more than 15 mass %.

[0120] <(C) Maleimide compound not having an aliphatic chain having 7 or more carbon atoms>

[0121] The resin composition of the present invention contains (C) a maleimide compound that does not have an aliphatic chain having 7 or more carbon atoms as a component other than (B). That is, when component (C) has an aliphatic chain, the aliphatic chain with the largest number of carbon atoms among these aliphatic chains has 6 or less carbon atoms. Component (C) may be used alone or in any combination of two or more.

[0122] In one embodiment, the component (C) preferably has a maleimide group directly bonded to a carbon atom constituting an aromatic ring. It is particularly preferred that the maleimide group contained in the component (C) is only a maleimide group directly bonded to a carbon atom constituting an aromatic ring.

[0123] In one embodiment, the maleimide compound of the component (C) preferably includes a maleimide compound represented by formula (C1-1) or (C1-2).

[0124] [Chemical Formula 14]

[0125]

[0126] [Where, B 2 Each independently represents a tetravalent organic group having no aliphatic chain having 7 or more carbon atoms, n represents an integer of 1 or more (preferably an integer of 1 to 100), A 3 Each independently represents a divalent organic group having no aliphatic chain having 7 or more carbon atoms, R 3 Each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, s represents an integer of 1 or more (preferably an integer of 1 or 1 to 100, more preferably an integer of 1 or 1 to 50, and further preferably an integer of 1 or 1 to 20), t each independently represents an integer of 0 to 2 (preferably 0), and other symbols are the same as in formula (B1)]. It should be noted that for each of the n unit, s unit and t unit, each unit may be the same or different.

[0127] B 2 Each independently represents a tetravalent organic group that does not have an aliphatic chain having 7 or more carbon atoms (that is, when having an aliphatic chain, the aliphatic chain with the largest number of carbon atoms among these aliphatic chains has 6 or less carbon atoms). 2 The backbone atoms of the "quaternary organic group" represented by B are selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms, and the number of backbone atoms is not particularly limited, and may be, for example, 5 to 3000, 5 to 1000, 5 to 100, or 5 to 50. 2 For example, it is a tetravalent group obtained by removing two anhydride groups (-CO-O-CO-) from a tetracarboxylic anhydride having no aliphatic chain having 7 or more carbon atoms, which is generally used as a raw material for polyimide, and is not particularly limited.

[0128] B 2 Each independently preferably is a tetravalent organic group that does not have an aliphatic chain having more than 7 carbon atoms and has an aromatic ring and / or a non-aromatic ring (that is, in the case of having an aliphatic chain, the aliphatic chain with the largest number of carbon atoms among these aliphatic chains has a carbon atom number of 6 or less and has an aromatic ring and / or a non-aromatic ring), and is more preferably a tetravalent group represented by the above formula (b3).

[0129] A 3 Each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms. 3The backbone atoms of the "divalent organic group" represented are selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms, and the number of backbone atoms is not particularly limited, and may be, for example, 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50.

[0130] The maleimide compound represented by the formula (C1-1) is preferably a maleimide compound represented by the formula (C2-1).

[0131] [Chemical Formula 15]

[0132]

[0133] [In the formula, each symbol is the same as in formula (C1-1), (b2) and (b3)].

[0134] The maleimide compound represented by formula (C1-1) is more preferably a maleimide compound represented by formula (C3-1),

[0135] [Chemical Formula 16]

[0136]

[0137] [Where R 2 Each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, each independently represents an integer of 0 to 2, and other symbols are the same as in formulas (C1-1), (b2) and (b3)]. It should be noted that for the f units, each unit may be the same or different.

[0138] The maleimide compound represented by the formula (C1-2) is preferably a maleimide compound represented by the formula (C2-2).

[0139] [Chemical Formula 17]

[0140]

[0141] [Where, X 3 Each independently represents a single bond, -C(R a )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, R a Each independently represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group, and ring Z x3 represents a non-aromatic ring which may have a group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, or an aromatic ring which may have a group selected from an alkyl group having 1 to 6 carbon atoms and a phenyl group, u each independently represents an integer greater than 0 or 1 (preferably an integer of 0 or 1 to 50), and other symbols are the same as in formula (C1-2)].

[0142] The maleimide compound represented by formula (C1-2) is more preferably a maleimide compound represented by formula (C3-2),

[0143] [Chemical Formula 18]

[0144]

[0145] [Where, X 4 Each independently represents a single bond, -C(R b )(R c )-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, R 4 and R b Each independently represents a hydrogen atom, a methyl group or a phenyl group, and R 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R c represents a hydrogen atom, a methyl group or a phenyl group, or R 5 and R c are combined with each other to form a ring (for example, an indane ring) which may have a group selected from an alkyl group and an alkenyl group, R 6 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, v represents an integer of 0 or more than 1 (preferably an integer of 0 or 1 to 10), and other symbols are the same as in formula (C1-2)]. It should be noted that for the u unit and the v unit, each unit may be the same or different.

[0146] Specific examples of the component (C) include maleimide compounds represented by formulae (C4-1) to (C4-4).

[0147] [Chemical Formula 19]

[0148]

[0149] [In the formula, n' or n" each independently represents an integer of 1 to 20 (preferably an integer of 1 to 10), s' represents an integer of 1 to 100 (preferably an integer of 1 to 50, more preferably an integer of 1 to 20), and v' each independently represents an integer of 1 to 10 (preferably an integer of 1 to 5)]. It should be noted that the order and respective configurations of n' units and n" units are arbitrary, including alternating copolymers, block copolymers, random copolymers, etc.

[0150] The weight average molecular weight (Mw) of the component (C) is not particularly limited, but is preferably from 200 to 50,000, more preferably from 300 to 40,000, further preferably from 400 to 20,000. The weight average molecular weight of the component (C) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0151] As a commercial item of (C)component, "BMI-6100" manufactured by Designer Molecules Co., Ltd., "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., etc. are mentioned, for example.

[0152] The content of (C) component in resin combination is not particularly limited. When the non-volatile component in resin combination is set to 100 mass %, it is preferably below 50 mass %, more preferably below 40 mass %, further more preferably below 30 mass %, more preferably below 25 mass %, and especially preferably below 20 mass %. The lower limit of the content of (C) component in resin combination is not particularly limited. When the non-volatile component in resin combination is set to 100 mass %, it is preferably more than 1 mass %, more preferably more than 3 mass %, further more preferably more than 5 mass %, further more preferably more than 10 mass %, and especially preferably more than 15 mass %.

[0153] The mass ratio of the component (C) to the component (B) in the resin composition (component (C) / component (B)) is not particularly limited, but is preferably at least 0.01, more preferably at least 0.1, further preferably at least 0.5, and particularly preferably at least 0.8. The upper limit of the mass ratio of the component (C) to the component (B) (component (C) / component (B)) is not particularly limited, but is preferably at most 50, more preferably at most 40, further more preferably at most 20, and particularly preferably at most 5.

[0154] The mass ratio of "component (A)" to "the total of component (B) and component (C)" in the resin composition (component (A) / the total of component (B) and component (C)) is not particularly limited, but is preferably at least 0.01, more preferably at least 0.05, further preferably at least 0.1, and particularly preferably at least 0.2. The upper limit of the mass ratio of component (A) to the total of component (B) and component (C) (component (A) / the total of component (B) and component (C)) is not particularly limited, but is preferably at most 5, more preferably at most 1, further preferably at most 0.5, and particularly preferably at most 0.3.

[0155] <(D) Any radical polymerizable compound>

[0156] The resin composition of the present invention may contain a radically polymerizable compound (D) other than the components (B) and (C) as an optional component. The component (D) may be used alone or in any combination of two or more.

[0157] (D) component can be, for example, a compound having a free radical polymerizable unsaturated group. As a free radical polymerizable unsaturated group, there is no particular limitation as long as it is free radical polymerizable. Preferably, it is an ethylenically unsaturated group having a carbon-carbon double bond at the end or inside, specifically, an unsaturated aliphatic group such as allyl, 3-cyclohexenyl; an aromatic group containing an unsaturated aliphatic group such as p-vinylphenyl, m-vinylphenyl, styryl; α, β-unsaturated carbonyl groups such as acryloyl, methacryloyl, maleoyl, fumaryl, etc. (D) component preferably has one or more free radical polymerizable unsaturated groups, more preferably two or more.

[0158] As the component (D), a wide range of known radical polymerizable compounds can be used without particular limitation, and examples thereof include (D-1) vinylphenyl radical polymerizable compounds and (D-2) (meth)acrylic radical polymerizable compounds.

[0159] <(D-1) Vinylphenyl radical polymerizable compound>

[0160] The (D-1) vinylphenyl-based radically polymerizable compound is a radically polymerizable compound having a vinylphenyl group. The (D-1) vinylphenyl-based radically polymerizable compound preferably has an average of at least two vinylphenyl groups per molecule.

[0161] In one embodiment, the (D-1) 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 a repeating unit represented by formula (D1) (the number of repeating units is preferably 2 to 300, more preferably 2 to 100) and a vinylbenzyl group (especially a vinylbenzyl-modified polyphenylene ether at both ends in which the hydrogen atoms of the hydroxyl groups at both ends of the polyphenylene ether are replaced by vinylbenzyl groups).

[0162] [Chemical Formula 20]

[0163]

[0164] [Where R 11 、R 12 、R 13 and R 14

[0065] 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.]

[0165] In another embodiment, the (D-1) vinylphenyl-based radically polymerizable compound is preferably a divinylbenzene polymer having a repeating unit represented by formula (D2) (the number of repeating units is preferably 2 to 200).

[0166] [Chemical Formula 21]

[0167]

[0168] [Where R 15 、R 16 and R 17

[0065] The divinylbenzene polymer may be a copolymer further comprising other styrene skeleton units such as styrene units and ethylstyrene units. In the case of comprising other styrene skeleton units, the ratio of the repeating unit of formula (D2) is preferably 5 to 70 mol% relative to all styrene skeleton units.

[0169] The number average molecular weight of the (D-1) vinylphenyl radical polymerizable compound is not particularly limited, but is preferably 500 to 100,000, more preferably 700 to 80,000. The number average molecular weight of component (D) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC). The vinyl functional group equivalent weight of the (D-1) vinylphenyl radical polymerizable compound is not particularly limited, but is preferably 200 to 3000 g / eq., more preferably 200 to 2000 g / eq.

[0170] Commercially available products of (D-1) vinylphenyl-based free radical polymerizable compounds include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-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.

[0171] <(D-2) (Meth)acrylic radical polymerizable compound>

[0172] The (D-2) (meth)acrylic radical polymerizable compound is a radical polymerizable compound having an acryloyl group and / or a methacryloyl group. The (D-2) (meth)acrylic radical polymerizable compound preferably has an average of 2 or more acryloyl groups and / or methacryloyl groups per molecule. The (D-2) (meth)acrylic radical polymerizable compound is preferably a (meth)acrylic modified polyphenylene ether having "acryloyl and / or methacryloyl groups" and a "polyphenylene ether skeleton", and is particularly preferably a (meth)acrylic modified polyphenylene ether having a repeating unit represented by formula (D3) (the number of repeating units is preferably 2 to 300, more preferably 2 to 100) and an acryloyl and / or methacryloyl group (particularly a (meth)acrylic modified polyphenylene ether in which the hydrogen atoms of the hydroxyl groups at both ends of the polyphenylene ether are replaced with acryloyl and / or methacryloyl groups at both ends).

[0173] [Chemical Formula 22]

[0174]

[0175] [Where R 21 、R 22 、R 23 and R 24

[0065] 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.]

[0176] The number average molecular weight of the (D-2) (meth)acrylic radical polymerizable compound is not particularly limited, but is preferably 500 to 10,000, more preferably 700 to 5,000. The functional group equivalent weight of the acryloyl and methacryloyl groups in the (D-2) (meth)acrylic radical polymerizable compound is not particularly limited, but is preferably 200 to 3,000 g / eq., more preferably 300 to 2,000 g / eq.

[0177] Examples of commercially available products of the (D-2) (meth)acrylic radical polymerizable compound include “SA9000” and “SA9000-111” (methacrylic acid-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

[0178] The content of (D) component in resin combination is not particularly limited. When the non-volatile component in resin combination is set to 100 mass %, it is preferably below 60 mass %, more preferably below 50 mass %, further more preferably below 40 mass %, more preferably below 30 mass %, and particularly preferably below 20 mass %. The lower limit of the content of (D) component in resin combination is not particularly limited. When the non-volatile component in resin combination is set to 100 mass %, it can be such as 0 mass %, more than 0.1 mass %, more than 1 mass %, more than 3 mass %, more than 5 mass %, more than 7 mass %, etc.

[0179] <(E) Inorganic fillers>

[0180] The resin composition of the present invention may contain (E) an inorganic filler as an optional component. The (E) inorganic filler is contained in the resin composition in the form of particles.

[0181] As the material of (E) inorganic filling material, an inorganic compound is used. As the material of (E) inorganic filling material, 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, zirconium tungstate phosphate, ferrite, iron alloy etc. can be mentioned. Among them, silicon dioxide is particularly preferred. As silicon dioxide, amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silica etc. can be mentioned. In addition, as silicon dioxide, spherical silicon dioxide is preferably used. (E) The inorganic filler may be used alone or in combination of two or more at any ratio.

[0182] Examples of commercially available inorganic fillers (E) include "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation, "YC100C," "YA050C," "YA050C-MJE," and "YA010C" manufactured by Yaduma Co., Ltd., "UFP-30" manufactured by DENKA Corporation, "SILFIL NSS-3N," "SILFIL NSS-4N," and "SILFIL NSS-5N" manufactured by Tokuyama Co., Ltd., "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Yaduma Co., Ltd., and "DAW-03" and "FB-105FD" manufactured by DENKA Corporation.

[0183] (E) The average particle size of the inorganic filler is not particularly limited, and is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, further preferably 1 μm or less, and particularly preferably 0.7 μm or less. (E) The lower limit of the average particle size of the inorganic filler is not particularly limited, and is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (E) 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 the inorganic filler can be prepared on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. The measurement sample can be a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a tube bottle 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 is set to blue and red. The volume-based particle size distribution of the inorganic filler is measured in a flow cell manner. The average particle size is calculated based on the obtained particle size distribution as the median particle size. As an example of a laser diffraction particle size distribution measuring device, the "LA-960" manufactured by Horiba, Ltd. can be mentioned.

[0184] (E) The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 (E) The upper limit of the specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 100 m 2 / g or less, preferably 70m 2 / g or less, more 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 sample surface using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area by the BET multipoint method.

[0185] (E) The 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 (E) inorganic filler material can be improved. As the surface treatment agent, for example, 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-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltri ... Acyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane and other methacrylic silane coupling agents; 3-acryloyloxypropyltrimethoxysilane and other acrylic silane coupling agents; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, Amino silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate 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 silane coupling agents such as 3-isocyanatepropyltriethoxysilane. silane coupling agents; anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic 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, and trifluoropropyltrimethoxysilane; and non-silane coupling alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane. Surface treatment agents may be used alone or in combination of two or more in any proportion.

[0186] Examples of commercially available surface treatment agents include "KBM-1003," "KBE-1003" (vinyl silane coupling agent), "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," and "KBM-575" manufactured by Shin-Etsu Chemical Co., Ltd. (amino silane coupling agent), "KBM-9659" (isocyanurate silane coupling agent), "KBE-585" (urea-based silane coupling agent), "KBM-802", "KBM-803" (mercapto silane coupling agent), "KBE-9007N" (isocyanate silane coupling agent), "X-12-967C" (anhydride silane coupling agent), "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling - alkoxysilane compound), etc.

[0187] From the viewpoint that the dispersibility of inorganic filler improves, the degree of the surface treatment carried out by surface treatment agent is preferably controlled within the scope of regulation.Specifically, preferably 100% by mass of inorganic filler has been surface treated by the surface treatment agent of 0.2% by mass to 5% by mass, more preferably 100% by mass of inorganic filler has been surface treated by the surface treatment agent of 0.2% by mass to 3% by mass, and further more preferably 100% by mass of inorganic filler has been surface treated by the surface treatment agent of 0.3% by mass to 2% by mass.

[0188] 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 2On the other hand, from the viewpoint of increasing the melt viscosity of the resin composition and preventing the increase in the melt viscosity in the sheet form, 1.0 mg / m 2 Below, more preferably 0.8mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0189] (E) 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 is added as a solvent to the inorganic filler 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 component, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0190] The content of (E) inorganic filler in resin combination is not particularly limited, and when the non-volatile component in resin combination is set to 100 mass %, it can be preferably below 90 mass %, more preferably below 80 mass %, further more preferably below 75 mass %, and especially preferably below 70 mass %. The lower limit of the content of (E) inorganic filler in resin combination is not particularly limited, and when the non-volatile component in resin combination is set to 100 mass %, it can be such as more than 0 mass %, more than 1 mass %, more than 5 mass %, more than 10 mass %, etc., it is preferably more than 20 mass %, more preferably more than 25 mass %, further more preferably more than 35 mass %, and especially preferably more than 40 mass %.

[0191] <(F) Curing accelerator>

[0192] The resin composition of the present invention may contain a curing accelerator (F) as an optional component. In one embodiment, the curing accelerator (F) may function as a catalyst for accelerating the addition reaction of component (A) with component (B) and component (C) (and component (D) when component (D) is included).

[0193] Examples of the curing accelerator (F) include imidazole curing accelerators (F-1), phosphorus curing accelerators (F-2), urea curing accelerators (F-3), guanidine curing accelerators (F-4), metal curing accelerators (F-5), and amine curing accelerators (F-6). In one embodiment, the curing accelerator (F) preferably includes the imidazole curing accelerator (F-1). The curing accelerators (F) may be used alone or in combination of two or more.

[0194] Examples of the imidazole curing accelerator (F-1) 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, 1-cyanoethyl-2-phenylimidazole, 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.

[0195] As the (F-1) imidazole curing accelerator, commercially available products may be used, and examples thereof include "1B2PZ", "2MZA-PW", and "2PHZ-PW" manufactured by Shikoku Chemicals Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0196] Examples of the phosphorus curing accelerator (F-2) include aliphatic phosphonium salts such as 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, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, and tetraphenylphosphonium bromide; Aromatic phosphonium salts such as p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; 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, Aliphatic phosphines such as di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexyl phosphine; dibutylphenyl phosphine, di-tert-butylphenyl phosphine, methyldiphenyl phosphine, ethyldiphenyl phosphine, butyldiphenyl phosphine, diphenylcyclohexyl phosphine, 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 Aromatic phosphines such as tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether are also included.

[0197] Examples of the urea curing accelerator (F-3) 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, and 3-(3,4-dimethylphenyl)- Aromatic dimethylureas such as 1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea].

[0198] Examples of the (F-4) 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.

[0199] Examples of the metal curing accelerator (F-5) include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, organozinc complexes such as zinc (II) acetylacetonate, organoferric complexes such as iron (III) acetylacetonate, organonickel complexes such as nickel (II) acetylacetonate, and organomanganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0200] Examples of the amine curing accelerator (F-6) include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo[5.4.0]undecene.

[0201] As the (F-6) amine-based curing accelerator, a commercially available item can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0202] The content of (F) curing accelerator in resin combination is not particularly limited. When the non-volatile component in resin combination is set to 100 mass %, it is better to be below 10 mass %, more preferably below 5 mass %, further more preferably below 3 mass %, and especially better to be below 1 mass %. The lower limit of the content of (F) curing accelerator in resin combination is not particularly limited. When the non-volatile component in resin combination is set to 100 mass %, it can be, for example, more than 0 mass %, more than 0.001 mass %, more than 0.01 mass %, more than 0.1 mass %, more than 0.5 mass % etc.

[0203] <(G) Other additives>

[0204] The resin composition of the present invention may further contain any additives as non-volatile components. Examples of such additives include: curing agents other than component (A), such as phenol curing agents and thiol curing agents; thermosetting resins such as epoxy resins, epoxy acrylate resins, urethane acrylate resins, polyurethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, silicone resins, and phenoxy resins; free radical polymerization initiators such as peroxide free radical polymerization initiators and azo free radical polymerization initiators; polyvinyl acetal resins, polyolefin resins, and the like. Thermoplastic resins such as hydrocarbon resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins; 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, olive green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and thiophene; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; bentonite, montmorillonite Thickeners such as silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; UV absorbers such as benzotriazole UV absorbers; adhesion enhancers such as urea silane; adhesion enhancers such as triazole adhesion enhancers, tetrazole adhesion enhancers, and triazine adhesion enhancers; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine surfactants and silicone surfactants; phosphorus flame retardants (such as phosphate esters) Flame retardants such as compounds, phosphazene compounds, phosphinic acid 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; stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic anhydride stabilizers, etc. (G) Other additives can be used alone or in combination of two or more in any proportion. Those skilled in the art can appropriately set the content of (G) other additives.

[0205] <(H) Organic solvents>

[0206] For the resin composition of the present invention, in addition to the non-volatile components mentioned above, it sometimes contains an arbitrary organic solvent as a volatile component. As the (H) organic solvent, a well-known organic solvent can be appropriately used, and its type is not particularly limited. As the (H) organic solvent, for example: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, carbitol acetate (ethyl diglycol (H) Organic solvents include, but are not limited to, ether ester solvents such as methyl 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; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) Organic solvents may be used alone or in combination of two or more in any proportions.

[0207] In one embodiment, the content of the organic solvent (H) is not particularly limited and can be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, based on 100% by mass of all components in the resin composition.

[0208] <Method for producing resin composition>

[0209] 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) an amine compound with a biphenyl skeleton, (B) a maleimide compound with a fatty chain having more than 7 carbon atoms, (C) a maleimide compound without a fatty chain having more than 7 carbon atoms, (D) any free radical polymerizable compound as needed, (E) an inorganic filler as needed, (F) a curing accelerator as needed, (G) other additives as needed, and (H) an organic solvent 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, the resin composition can be stirred or vibrated using a stirring device or an oscillating device such as a mixer to uniformly disperse it. In addition, deaeration can be performed under low pressure conditions such as under vacuum while stirring or vibrating.

[0210] <Characteristics of the resin composition>

[0211] The resin composition of the present invention comprises (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a maleimide compound not having an aliphatic chain having 7 or more carbon atoms. By using such a resin composition, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df) and excellent peel strength of the plated conductor layer can be obtained.

[0212] 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 shown in the following Test Example 1 can be preferably 0.020 or less, 0.010 or less, more preferably 0.008 or less, 0.007 or less, further preferably 0.006 or less, 0.005 or less, and particularly preferably 0.004 or less, 0.003 or less.

[0213] 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 shown in the following Test Example 1 can be preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, further more preferably 3.0 or less, and particularly preferably 2.9 or less.

[0214] The cured product of the resin composition of the present invention can have excellent peel strength of the plated conductor layer. Therefore, in one embodiment, as shown in Test Example 2 below, a copper-plated conductor layer is formed on the cured product, and the peel strength of the copper plating layer calculated based on the load when the copper-plated conductor layer is peeled off in a vertical direction can be preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, further preferably 0.35 kgf / cm or more, and particularly preferably 0.4 kgf / cm or more. There is no particular upper limit, and it can be, for example, 10 kgf / cm or less.

[0215] In one embodiment, the cured product of the resin combination of the present invention can have the feature that the arithmetic mean roughness (Ra) of the surface after roughening treatment is low. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the cured product surface after roughening treatment measured as shown in following Test Example 2 can become preferably below 300nm, more preferably below 200nm, further more preferably below 150nm, further more preferably below 120nm, particularly preferably below 100nm. There is no particular restriction on the lower limit, and it can be set to more than 1nm, more than 2nm, etc.

[0216] <Applications of the resin composition>

[0217] 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 (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 redistribution layer), and the conductor layer is formed on the insulating layer. In addition, in a printed wiring board described later, it can be suitably used as: a resin composition for forming the insulating layer of a printed wiring board (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 the applications requiring a resin composition such as a sheet-like laminate such as a resin sheet, a prepreg, a solder resist, an underfill material, a chip bonding material, a semiconductor sealing material, a filling resin (hole-filling resin), and a component embedding resin.

[0218] 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 redistribution forming layer (resin composition for redistribution forming layer formation) as an insulating layer for forming a redistribution layer, and a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing). When manufacturing a semiconductor chip package, a redistribution layer can be further formed on the sealing layer.

[0219] (1) a step of laminating a temporary fixing film on a substrate,

[0220] (2) a process of temporarily fixing the semiconductor chip on a temporary fixing film,

[0221] (3) a step of forming a sealing layer on a semiconductor chip,

[0222] (4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip,

[0223] (5) forming a rewiring forming 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

[0224] (6) A step of forming a rewiring layer as a conductive layer on the rewiring formation layer.

[0225] Furthermore, the resin composition of the present invention provides an insulating layer having excellent component embedding properties, and therefore can be suitably used also when the printed wiring board is a component-embedded circuit board.

[0226] <Sheet-like laminated materials>

[0227] The resin composition of the present invention can also be used by coating in a varnish state, but is usually preferably used industrially in the form of a sheet-like laminate containing the resin composition.

[0228] As the sheet-like laminated material, the following resin sheets and prepregs are preferred.

[0229] In one embodiment, a resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

[0230] From the viewpoint of thinning of printed wiring board and the cured product of the resin composition that can provide excellent insulating properties as a 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 more than 5 μm, more than 10 μm, etc.

[0231] Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0232] When a film formed of a plastic material is used as the support, examples of the plastic material include 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, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0233] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of copper alone or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0234] The surface of the support that contacts the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

[0235] 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 commercially available product, for example, "SK-1", "AL-5", "AL-7" made by Lintec Co., Ltd., a PET film with a release layer having an alkyd resin release agent as a main component, "Lumirror T60" made by Toray Industries, Ltd., "Purex" made by Teijin Co., Ltd., "Unipeel" made by UNITIKA Co., Ltd., etc.

[0236] 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 within the above range.

[0237] In one embodiment, the resin sheet may further include an arbitrary layer as needed. As the arbitrary layer, for example, a protective film selected according to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the opposite side of the support) 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.

[0238] 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, followed by drying to form a resin composition layer.

[0239] Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. The organic solvents may be used alone or in combination of two or more.

[0240] Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The drying conditions vary depending on the boiling point of the organic solvent in the resin composition or resin varnish. For example, when using a resin composition or resin varnish containing 30% to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0241] The resin sheet can be stored in a roll. If the resin sheet has a protective film, the protective film can be peeled off before use.

[0242] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

[0243] The sheet-like fiber substrate used in the prepreg is not particularly limited, and materials commonly used as prepreg substrates, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the perspective of reducing the thickness of 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.

[0244] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0245] The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0246] 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 more suitably used to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

[0247] <Printed wiring board>

[0248] 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.

[0249] Regarding the printed wiring board, for example, the above-mentioned resin sheet can be used to produce it by a method including the following steps (I) and (II);

[0250] (I) a step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate, and (II) a step of curing (eg, thermally curing) the resin composition layer to form an insulating layer.

[0251] The "inner substrate" used in step (I) refers to a component 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, and a thermosetting polyphenylene ether substrate. 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 to be further formed with an insulating layer and / or a conductor layer 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 component-built-in circuit board, an inner substrate with built-in components can be used.

[0252] The inner substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet onto the inner substrate from the support body side. As a member for heat-pressing the resin sheet onto 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 preferable not to press the heat-pressing member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface unevenness of the inner substrate.

[0253] The inner layer substrate and the resin sheet can be laminated by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably 80°C to 140°C, the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7hPa or less.

[0254] Lamination can be performed using a commercially available vacuum laminator, such as 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.

[0255] After lamination, the laminated resin sheet can be smoothed by pressing the heat-pressed component under normal pressure (atmospheric pressure), for example, from the support side. 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 lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0256] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0257] In step (II), the resin composition layer is cured (e.g., thermally cured) to form an insulating layer composed of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions commonly used in forming insulating layers of printed wiring boards can be used.

[0258] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, but 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 is preferably 5 to 120 minutes, more preferably 10 to 100 minutes, and further preferably 15 to 100 minutes.

[0259] The resin composition layer may be preheated at a temperature lower than the curing temperature before thermally curing the resin composition layer. For example, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, and more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes before thermally curing the resin composition layer.

[0260] When manufacturing a printed wiring board, the process of (III) opening a hole in the insulating layer, the process of (IV) roughening the insulating layer, and the process of (V) forming a conductor layer can be further implemented. These processes (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 process (II), the removal of the support can be implemented between process (II) and process (III), between process (III) and process (IV), or between process (IV) and process (V). In addition, as needed, the formation of the insulating layer and the conductor layer of process (II) to process (V) can also be repeatedly implemented to form a multilayer wiring board.

[0261] 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 when using a resin sheet.

[0262] Step (III) is a step of drilling holes in the insulating layer. This allows the formation of holes such as through holes and through holes in the insulating layer. Step (III) can be carried out using, for example, a drill, laser, or plasma, depending on the composition of the resin composition used to form the insulating layer. The size and shape of the holes can be appropriately determined based on the design of the printed wiring board.

[0263] Step (IV) is a step of roughening the insulating layer. Typically, smear removal is also performed in step (IV). The steps and conditions for the roughening treatment are not particularly limited, and known steps and conditions commonly used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution.

[0264] There are no particular restrictions on the swelling liquid used in the roughening treatment, and examples include alkaline solutions, surfactant solutions, and the like. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd. There are no particular restrictions on the swelling treatment based on the swelling liquid, and for example, the insulating layer can be immersed 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 preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0265] As the oxidizing agent 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 oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent 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% by mass to 10% by mass. As commercially available oxidizing agents, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited.

[0266] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd.

[0267] Treatment with a neutralizing solution can be performed by immersing the surface roughened with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the perspective of operability, a method in which the surface roughened with an oxidizing agent is immersed in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes is preferred.

[0268] In one embodiment, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. There is no particular restriction on the lower limit, and it can be, for example, 1 nm or more, 2 nm or more. The root mean square roughness (Rq) can be measured using a non-contact surface roughness meter.

[0269] Step (V) is a step of forming a conductor layer, in which 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 mentioned. Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of the formation of the conductor layer, preferably 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, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, and further preferably a single metal layer of copper.

[0270] The conductive layer may have a single-layer structure or a multilayer structure comprising two or more single metal layers or alloy layers formed of different metals or alloys. When the conductive layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

[0271] 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.

[0272] In one embodiment, the conductor layer can be formed by plating. For example, a conventionally known technique such as a semi-additive method or a fully additive method can be used to plate the surface of the insulating layer to form a conductor layer having a desired wiring pattern. From the perspective of ease of production, formation using a semi-additive method is preferred. An example of forming a conductor layer using a semi-additive method is shown below.

[0273] First, a plating seed layer is formed on the surface of the insulating layer using electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer using electrolytic plating, and the mask pattern is then removed. The unnecessary plating seed layer is then removed using etching or other methods, forming a conductor layer having the desired wiring pattern.

[0274] In other embodiments, the conductor layer can be formed using metal foil. When a metal foil is used to form the conductor layer, process (V) is preferably implemented between process (I) and process (II). For example, after process (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 process (I). Next, process (II) is implemented to form an insulating layer. Then, utilizing the metal foil on the insulating layer, a conductor layer with a desired wiring pattern can be formed using conventionally known techniques such as a subtractive method and an improved semi-additive method.

[0275] Metal foil can be produced by known methods such as electrolysis and 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.

[0276] Semiconductor devices

[0277] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0278] Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and aircraft).

[0279] Example

[0280] The present invention is described in detail below by way of examples. The present invention is not limited to these examples. It should be noted that, unless otherwise specified, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass," respectively. Unless otherwise specified, the temperature is room temperature (25°C).

[0281] <Example 1>

[0282] 10 parts of a biphenyl skeleton-containing amine compound ("BAN" manufactured by Nippon Kayaku Co., Ltd.), 20 parts of an aliphatic maleimide compound ("BMI-689" manufactured by Designer Molecules Co., Ltd.), 28.6 parts of an aromatic maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution having a solid content of 70%), 1 part of an imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Co., Ltd., 1-benzyl-2-phenylimidazole), 60 parts of spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m2) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) were mixed. 2 / g) were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a resin composition.

[0283] <Example 2>

[0284] A resin composition was prepared in the same manner as in Example 1 except that 20 parts of the aliphatic maleimide compound ("BMI-1500" manufactured by Designer Molecules) was used instead of 20 parts of the aliphatic maleimide compound ("BMI-689" manufactured by Designer Molecules).

[0285] <Example 3>

[0286] A resin composition was prepared in the same manner as in Example 1 except that 20 parts of the aliphatic maleimide compound ("BMI-2500" manufactured by Designer Molecules) was used instead of 20 parts of the aliphatic maleimide compound ("BMI-689" manufactured by Designer Molecules).

[0287] <Example 4>

[0288] A resin composition was prepared in the same manner as in Example 1 except that 20 parts of the aliphatic maleimide compound ("BMI-3000J" manufactured by Designer Molecules) was used instead of 20 parts of the aliphatic maleimide compound ("BMI-689" manufactured by Designer Molecules).

[0289] <Example 5>

[0290] A resin composition was prepared in the same manner as in Example 2 except that 20 parts of an aromatic maleimide compound ("BMI-6100" manufactured by Designer Molecules) was used instead of 28.6 parts of an aromatic maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.).

[0291] <Example 6>

[0292] A resin composition was prepared in the same manner as in Example 3 except that 20 parts of an aromatic maleimide compound ("BMI-6100" manufactured by Designer Molecules) was used instead of 28.6 parts of an aromatic maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.).

[0293] <Example 7>

[0294] A resin composition was prepared in the same manner as in Example 2, except that the amount of the aromatic maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with a solid content of 70%) was changed from 28.6 parts to 14.3 parts, and 10 parts of the aromatic maleimide compound ("BMI-6100" manufactured by Designer Molecules) was further used.

[0295] <Example 8>

[0296] A MEK solution (70% by mass of non-volatile content) of a maleimide compound A (Mw / Mn = 1.81, v" = 1.47 (mainly 1, 2, or 3)) represented by the following formula (X) synthesized by the method described in Synthesis Example 1 of Japan Invention Association Publication No. 2020-500211 was prepared.

[0297] [Chemical Formula 23]

[0298]

[0299] A resin composition was prepared in the same manner as in Example 2, except that 28.6 parts of an aromatic maleimide compound (maleimide compound A represented by formula (X), a MEK solution with a solid content of 70% by mass) was used instead of 28.6 parts of an aromatic maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with a solid content of 70%).

[0300] <Example 9>

[0301] A resin composition was prepared in the same manner as in Example 2, except that the amount of spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd.) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) was changed from 60 parts to 70 parts, and 15.4 parts of vinylbenzyl-modified polyphenylene ether ("OPE-2St2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a solid content of 65%) was further used.

[0302] <Example 10>

[0303] A resin composition was prepared in the same manner as in Example 2, except that the amount of spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd.) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) was changed from 60 parts to 70 parts, and 20 parts of methacrylate-modified polyphenylene ether (a toluene solution containing "SA9000-111" manufactured by SABIC Innovative Plastics having a solid content of 50%) was further used.

[0304] <Example 11>

[0305] A resin composition was prepared in the same manner as in Example 2, except that the amount of spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd.) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) was changed from 60 parts to 70 parts, and 15.4 parts of a divinylbenzene / styrene copolymer ("ODV-XET-X04" manufactured by Nippon Steel Chemical Materials Co., Ltd., a toluene solution with a solid content of 65%) was further used.

[0306] <Comparative Example 1>

[0307] A resin composition was prepared in the same manner as in Example 1, except that 20 parts of the aliphatic maleimide compound ("BMI-689" manufactured by Designer Molecules) was not used and the amount of the aromatic maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with a solid content of 70%) was changed from 28.6 parts to 57.1 parts.

[0308] Comparative Example 2

[0309] A resin composition was prepared in the same manner as in Example 1, except that the amount of the aliphatic maleimide compound ("BMI-689" manufactured by Designer Molecules) used was changed from 20 parts to 10 parts, and 10 parts of an amine compound not containing a biphenyl skeleton ("AA" manufactured by Nippon Kayaku Co., Ltd.) were used instead of 10 parts of an amine compound containing a biphenyl skeleton ("BAN" manufactured by Nippon Kayaku Co., Ltd.).

[0310] <Test Example 1: Measurement of Relative Permittivity (Dk) and Dielectric Loss Tangent (Df)>

[0311] A polyethylene terephthalate film ("AL5" manufactured by Lintec Co., Ltd., 38 μm thick) with a release layer was prepared as a support. The resin composition obtained in the Examples and Comparative Examples was evenly coated onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. The resin composition was then dried at 80°C to 100°C (90°C on average) for 4 minutes to obtain a resin sheet A comprising a support and a resin composition layer.

[0312] The resulting resin sheet A was cured in an oven at 190°C for 90 minutes. Resin sheet A was removed from the oven, and the support was peeled off from the resin sheet A to obtain a cured product of the resin composition layer. This cured product was cut into pieces 80 mm in length and 2 mm in width to form a cured product B for evaluation.

[0313] The dielectric constant (Dk value) and dielectric loss tangent (Df value) of the evaluation cured product B were measured using an Agilent Technologies "HP8362B" by the cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The measurements were performed on two test pieces, and the average values ​​were calculated.

[0314] <Test Example 2: Measurement of Peel Strength and Arithmetic Average Roughness (Ra)>

[0315] (1) Preparation of inner substrate

[0316] Both sides of 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 Corporation) with an inner layer circuit formed thereon were etched 1 μm using a microetchant ("CZ8101" manufactured by MEC Corporation) to roughen the copper surface.

[0317] (2) Lamination of resin sheet A

[0318] The resin sheet A obtained in Test Example 1 was laminated onto both surfaces of the inner-layer substrate using a batch vacuum press laminator (Nikko Materials Co., Ltd., 2-Stage Buildup Laminator "CVP700"), with the resin composition layer in contact with the inner-layer substrate. Lamination was performed by reducing the pressure for 30 seconds to adjust the pressure to 13 hPa or less, then pressing at 120°C at a pressure of 0.74 MPa for 30 seconds. Subsequently, hot pressing was performed at 100°C at a pressure of 0.5 MPa for 60 seconds.

[0319] (3) Thermal curing of the resin composition layer

[0320] The inner layer substrate laminated with resin sheet A was then placed in a 130°C oven and heated for 30 minutes. The resin composition layer was then thermally cured in a 190°C oven and an insulating layer was formed. The support was then peeled off, yielding a cured substrate A comprising an insulating layer, an inner layer substrate, and an insulating layer in this order.

[0321] (4) Roughening treatment

[0322] 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.

[0323] (Wet decontamination treatment)

[0324] 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, followed by immersion in an oxidizing solution ("Concentrate Compact CP" manufactured by Atotech Japan, an aqueous solution of approximately 6% potassium permanganate and 4% sodium hydroxide) at 80°C for 20 minutes. Subsequently, the substrate 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, followed by drying at 80°C for 15 minutes.

[0325] (5) Measurement of the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment

[0326] The arithmetic mean roughness (Ra) of the insulating layer surface of the cured substrate A after roughening treatment was determined from the numerical values ​​obtained using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bruker) in VSI mode with a 50x lens and a measurement range of 121 μm × 92 μm. The measurement was performed by averaging 10 points.

[0327] (6) Formation of Conductor Layer

[0328] A conductor layer was formed on the roughened surface of the insulating layer of cured substrate A using a semi-additive process. Specifically, the roughened substrate was 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. Subsequently, the substrate was heated at 150°C for 30 minutes and annealed to form a resist layer, which was then patterned by etching. Subsequently, copper sulfate electroplating was performed to form a 25μm thick conductor layer, which was then annealed at 190°C for 60 minutes. The resulting substrate is referred to as "evaluation substrate B."

[0329] (7) Determination of peel strength of plated conductor layer

[0330] The peel strength between the insulation layer and the conductor layer was measured in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a 10 mm wide and 100 mm long cut was made in the conductor layer of evaluation substrate B. One end of the cut was peeled off and clamped with a clamp. The load (kgf / cm) when the cut was vertically peeled off 35 mm at a speed of 50 mm / min at room temperature was measured to determine the peel strength. A tensile testing machine ("AC-50C-SL" manufactured by TSE Co., Ltd.) was used for the measurement.

[0331] 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.

[0332] [Table 1]

[0333]

[0334] As can be seen from the above, by using a resin composition containing (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a maleimide compound not having an aliphatic chain having 7 or more carbon atoms, a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df) and excellent peel strength of the plated conductor layer can be obtained.

Claims

1. A resin composition comprising: (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, (C) a maleimide compound having no aliphatic chain having 7 or more carbon atoms, and (E) inorganic filler materials, Component (A) comprises an amine compound having a repeating unit represented by formula (A1), In the formula, V and W each independently represent -C(R')2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, R each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent, and h, i, and j each independently represent an integer from 0 to 2; Component (B) contains a maleimide compound represented by formula (B1), Where, A 1 Each independently represents a divalent organic group having an aliphatic chain having 7 or more carbon atoms, A 2 Each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms, B 1 Each independently represents a tetravalent organic group having an aromatic ring and / or a non-aromatic ring, n1 and n2 represent integers of 0 or 1 or greater, Either m1 or m2 represents 1 and the other represents 0, The sum of n1 and m1 is 1 or greater; The component (C) contains a maleimide compound represented by formula (C1-1) or (C1-2), Where, A 2 Each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms, B 2 Each independently represents a tetravalent organic group having no aliphatic chain having 7 or more carbon atoms, n represents an integer greater than or equal to 1, A 3 Each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms, R 3 Each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, s represents an integer of 1 or greater, t each independently represents an integer from 0 to 2; When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 5% by mass or more. The mass ratio of the component (A) to the total of the components (B) and (C) (component (A) / the total of the components (B) and (C)) is 0.1 to 0.3, and the content of the component (E) is 40 to 80 mass % based on 100 mass % of the nonvolatile matter in the resin composition.

2. 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.

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 (B) is 1% 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 (B) is 50% by mass or less.

5. 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 3% by mass to 40% by mass. 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 more.

7. 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 20% by mass or less.

8. 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 1% by mass or more.

9. 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 50% by mass or less.

10. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (C) is 3 mass % to 40 mass %.

11. 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 15% 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 (C) is 20% by mass or less.

13. The resin composition according to claim 1, wherein The mass ratio of the component (C) to the component (B) (component (C) / component (B)) is 0.01 or more.

14. The resin composition according to claim 1, wherein The mass ratio of the component (C) to the component (B) (component (C) / component (B)) is 50 or less.

15. The resin composition according to claim 1, wherein The mass ratio of the component (C) to the component (B) (component (C) / component (B)) is 0.5 to 20.

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

17. The resin composition according to claim 1, wherein The mass ratio of the component (C) to the component (B) (component (C) / component (B)) is 5 or less.

18. The resin composition according to claim 1, wherein The mass ratio of the component (A) to the total of the component (B) and the component (C) (component (A) / the total of the component (B) and the component (C)) is 0.2 to 0.

3.

19. The resin composition according to claim 1, wherein (D) A radical polymerizable compound other than the (B) component and the (C) component is further contained.

20. The resin composition according to claim 19, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 0.1% by mass or more.

21. The resin composition according to claim 19, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 7% by mass or more.

22. The resin composition according to claim 19, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 30% by mass or less.

23. The resin composition according to claim 19, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 20% by mass or less.

24. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the (E) component is 40 mass % or more and 70 mass % or less.

25. The resin composition according to claim 1, wherein When measured under the conditions of 5.8 GHz and 23° C., the dielectric loss tangent of the cured product of the resin composition is 0.020 or less.

26. The resin composition according to claim 1, wherein When measured under the conditions of 5.8 GHz and 23° C., the dielectric loss tangent of the cured product of the resin composition is 0.004 or less.

27. The resin composition according to claim 1, wherein When measured under the conditions of 5.8 GHz and 23° C., the dielectric loss tangent of the cured product of the resin composition is 0.003 or less.

28. The resin composition according to claim 1, wherein When measured under the conditions of 5.8 GHz and 23° C., the relative dielectric constant of the cured product of the resin composition is 5.0 or less.

29. The resin composition according to claim 1, wherein When measured under the conditions of 5.8 GHz and 23° C., the relative dielectric constant of the cured product of the resin composition is 2.9 or less. 30 . A cured product comprising 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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