resin composition

Abstract

To provide a resin composition that yields a cured product capable of sustaining superior copper foil adhesive strength even after a highly accelerated stress test (HAST) and also having a high glass transition temperature.SOLUTION: A resin composition comprises (A) a maleimide resin and (B) an acid salt of an amine compound represented by formula (I). In formula (I), R1, R2, R3, R4, and R5 independently represent a hydrogen atom or a substituent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition containing maleimide resin. Furthermore, it relates to a resin sheet, a printed circuit board, and a semiconductor device obtained using the resin composition. [Background technology]

[0002] A known manufacturing technique for printed circuit boards is the build-up method, in which insulating layers and conductive layers are stacked alternately. In the build-up method, the insulating layer is formed, for example, by curing a resin composition containing maleimide resin.

[0003] Generally, maleimide resins have low dielectric properties, but using pyridine-based curing accelerators resulted in low adhesion strength after accelerated environmental testing (HAST). On the other hand, using imidazole-based curing accelerators avoids the above problem, but their low catalytic activity resulted in a low glass transition temperature (Tg). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 7197067 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a resin composition that can obtain a cured product that maintains excellent copper foil adhesion strength even after accelerated environmental testing (HAST) and has a high glass transition temperature. [Means for solving the problem]

[0006] In order to achieve the objectives of the present invention, the inventors conducted diligent studies and, as a result, unexpectedly discovered that by including an acid salt of an amine compound represented by formula (I) described below in the maleimide resin composition, it is possible to suppress the diffusion of water into the resin, prevent the progression of oxidation due to heat and water in accelerated environmental testing (HAST), maintain excellent copper foil adhesion strength even after accelerated environmental testing (HAST), and obtain a cured product with a high glass transition temperature. This led to the completion of the present invention.

[0007] In other words, the present invention includes the following: [1] (A) Maleimide resin, and (B) Formula (I):

[0008] [ka]

[0009] [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 Each of these independently represents either a hydrogen atom or a substituent. A resin composition containing an amine compound salt represented by [formula]. [2] The resin composition according to [1] above, wherein the amine compound represented by formula (I) is 4-dimethylaminopyridine. [3] The resin composition according to [1] or [2] above, wherein component (B) comprises a salt of an amine compound represented by formula (I) and an organic acid selected from carboxylic acids and sulfonic acids. [4] Component (B) is an amine compound represented by formula (I) and formulas (IIa) to (IIc):

[0010] [ka]

[0011] [In the formula, X represents -CO- or -SO2-; R a , R b, R c , R d , R e , R f and R g each independently represent a hydrogen atom or a substituent.]] The resin composition according to any one of the above [1] to [3], comprising a salt with an organic acid represented by any one of [5] The resin composition according to any one of the above [1] to [4], wherein component (B) comprises a salt of an amine compound represented by formula (I) and an organic acid having an acid dissociation constant in water at 25°C (pK a a); in the case of a polyvalent organic acid, the lowest first-stage acid dissociation constant (pK a1 a)) of 3.0 or less. [6] The resin composition according to any one of the above [1] to [5], wherein component (B) comprises a salt of an amine compound represented by formula (I) and an organic acid selected from phthalic acid, trimellitic acid and p-toluenesulfonic acid. [7] The resin composition according to any one of the above [1] to [6], wherein the mass ratio of component (B) to component (A) (content of component (B) / content of component (A)) is 0.001 to 0.1. [8] The resin composition according to any one of the above [1] to [7], further comprising (C) an inorganic filler. [9] The resin composition according to the above [8], wherein component (C) comprises silica.

[10] The resin composition according to the above [8] or [9], wherein the content of component (C) is 40% by mass or more, when the non-volatile component in the resin composition is taken as 100% by mass.

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

[10] , wherein the content of (D) an anionic polymerizable curing agent is 0% by mass to 20% by mass, when the non-volatile component in the resin composition is taken as 100% by mass.

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

[11] , wherein the content of (E) an epoxy resin is 0% by mass to 20% by mass, when the non-volatile component in the resin composition is taken as 100% by mass.

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

[12] , wherein the content of (F) a thermoplastic resin is 0% by mass to 30% by mass, when the non-volatile component in the resin composition is taken as 100% by mass.

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

[13] above, wherein the glass transition temperature (Tg) of the cured product of the resin composition is 140°C or higher.

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

[14] above, for forming an insulating layer on a printed circuit board.

[16] A cured product of any of the resin compositions described in [1] to

[15] above.

[17] A resin sheet having a support and a resin composition layer formed from any of the resin compositions described in [1] to

[15] above, provided on the support.

[18] A printed circuit board comprising an insulating layer made of a cured resin composition described in any of [1] to

[15] above.

[19] A semiconductor device including the printed circuit board described in

[18] above.

[20] Equation (I):

[0012] [ka]

[0013] [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 Each of these independently represents either a hydrogen atom or a substituent. A maleimide resin curing accelerator containing an amine compound salt represented by [formula]. [Effects of the Invention]

[0014] According to the resin composition of the present invention, it is possible to obtain a cured product that maintains excellent copper foil adhesion strength even after accelerated environmental testing (HAST) and has a high glass transition temperature. [Modes for carrying out the invention]

[0015] The present invention will be described in detail below with reference to its preferred embodiments. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with modifications as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0016] <Resin composition> The resin composition of the present invention comprises (A) a maleimide resin and (B) an acid salt of an amine compound represented by formula (I). With such a resin composition, it is possible to obtain a cured product that maintains excellent copper foil adhesion strength even after accelerated environmental testing (HAST) and has a high glass transition temperature.

[0017] The resin composition of the present invention may further contain any optional components in addition to (A) a maleimide resin and (B) an acid salt of an amine compound represented by formula (I). Examples of optional components include (C) an inorganic filler, (D) an anionic curing agent, (E) an epoxy resin, (F) a thermoplastic resin, and (G) a radical polymerization initiator.

[0018] The following provides a detailed explanation of each component included in the resin composition.

[0019] <(A) Maleimide resin> The resin composition of the present invention contains (A) a maleimide resin. (A) The maleimide resin may be used alone or in combination of two or more types. (A) The maleimide resin has one or more maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl groups) per molecule.

[0020] (A) The maleimide resin may be an aromatic maleimide resin having a maleimide group directly bonded to the aromatic ring, or an aliphatic maleimide resin not having a maleimide group directly bonded to the aromatic ring, but it is preferable that it contains an aromatic maleimide resin.

[0021] (A) Maleimide resins are not particularly limited, but examples include maleimide resins having a biphenyl skeleton, maleimide resins having an indane skeleton, maleimide resins having a bismaleimidediphenylmethane skeleton, maleimide resins having a carbon skeleton derived from dimer acid, and maleimide resins having an aromatic polyetherketone skeleton.

[0022] The carbon skeleton derived from dimer acid refers to a carbon skeleton obtained by removing the two terminal carboxyl groups (-COOH) of dimer acid, or a carbon skeleton obtained by replacing the two terminal carboxyl groups (-COOH) with methylene groups (-CH2-). Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those with 11 to 22 carbon atoms, more preferably those with 14 to 20 carbon atoms, and particularly preferably those with 18 carbon atoms), and its industrial production process is largely standardized in the industry. Dimer acid is readily available, especially those mainly composed of 36-carbon dimer acid obtained by dimerizing 18-carbon unsaturated fatty acids such as oleic acid and linoleic acid, which are inexpensive and readily available. In addition, dimer acid may contain arbitrary amounts of monomeric acids, trimeric acids, and other polymerized fatty acids depending on the production method, degree of purification, etc. Furthermore, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrogenated products obtained by further hydrogenation to reduce the degree of unsaturation are also included as dimer acid.

[0023] Maleimide resins having a carbon skeleton derived from dimer acid are given by formula (1):

[0024] [ka]

[0025] [In the formula, Each of the n+1 X independently represents a divalent organic group consisting of five or more skeletal atoms selected from carbon atoms, nitrogen atoms (that do not form imides), oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms, and at least one of the n+1 X represents a divalent hydrocarbon group derived from a dimer acid; Each of the n Y groups independently represents a tetravalent organic group consisting of five or more skeletal atoms selected from carbon atoms, nitrogen atoms (that do not form imides), oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; n represents an integer of 0 or greater than or equal to 1. It is preferable that the maleimide resin represented by [formula] is included.

[0026] Each of the n+1 X independently represents a divalent organic group consisting of five or more (preferably 5 to 200, more preferably 5 to 100, and even more preferably 5 to 50) skeletal atoms selected from carbon atoms, nitrogen atoms (that do not form imides), oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms, and at least one of the n+1 X represents a divalent hydrocarbon group derived from a dimer acid.

[0027] Halogen atoms are fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms.

[0028] A divalent hydrocarbon group derived from dimer acid refers to a divalent hydrocarbon group obtained by removing the two terminal carboxyl groups (-COOH) of a dimer acid, or a divalent hydrocarbon group obtained by replacing the two terminal carboxyl groups (-COOH) with methylene groups (-CH2-).

[0029] The n+1 X atoms may have divalent organic groups other than divalent hydrocarbon groups derived from dimer acid, but when the n+1 X atoms are considered as 100 mol%, it is preferable that 30 mol% or more of them are divalent hydrocarbon groups derived from dimer acid, more preferably that 60 mol% or more are divalent hydrocarbon groups derived from dimer acid, even more preferably that 90 mol% or more are divalent hydrocarbon groups derived from dimer acid, and it is particularly preferable that all n+1 X atoms are divalent hydrocarbon groups derived from dimer acid.

[0030] The divalent organic groups in the n+1 X, other than the divalent hydrocarbon groups derived from the dimer acid, may be divalent organic groups without an aromatic ring, or they may be divalent organic groups having an aromatic ring.

[0031] Each of the n Y independently represents a tetravalent organic group consisting of five or more (preferably 5 to 200, more preferably 5 to 100, and even more preferably 5 to 50) skeletal atoms selected from carbon atoms, nitrogen atoms (that do not form imides), oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms. The tetravalent organic group represented by Y may be a tetravalent organic group without an aromatic ring, or a tetravalent organic group having an aromatic ring.

[0032] In one embodiment, the tetravalent organic group represented by Y is preferably of formula (Y1) to (Y5):

[0033] [ka]

[0034] [In the formula, Ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 Each independently represents an aromatic ring which may have substituents, or an unaromatic ring which may have substituents; Y 2a , Y 3a , Y 3b , Y 4a , Y 4b , Y 4c , Y 5a , Y 5b , Y 5c and Y 5d These are, independently, single bonds, -C(R y ) indicates -2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R yEach independently represents an alkyl group which may be substituted with a hydrogen atom or a halogen atom, or two R atoms bonded to the same carbon atom. y They combine and bond to form a non-aromatic ring which may have substituents; * indicates the binding site. The group is selected from among these. Note that the two bonding sites on the same ring represented by * are bonding sites with two adjacent carbon atoms on that ring, respectively.

[0035] Ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 Each independently represents an aromatic ring which may have substituents, or an aromatic ring which may have substituents; in one embodiment, preferably an aromatic ring which may have substituents, more preferably an aromatic ring which may have substituents, and even more preferably an alkyl-substituted benzene ring.

[0036] An aromatic ring refers to a ring that follows Hückel's rule, where the number of electrons in the π-electron system on the ring is 4p+2 (where p is a natural number). An aromatic ring can be an aromatic carbocyclic ring, which consists only of carbon atoms, or an aromatic heterocyclic ring, which has heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms. In one embodiment, an aromatic carbocyclic ring is preferred. In one embodiment, an aromatic ring with 5 to 14 members is preferred, an aromatic ring with 6 to 14 members is more preferred, and an aromatic ring with 6 to 10 members is even more preferred. Suitable specific examples of aromatic rings (aromatic carbocyclic rings) include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, etc., more preferably benzene rings or naphthalene rings, and particularly preferably benzene rings.

[0037] A non-aromatic ring refers to a ring other than an aromatic ring, which has aromaticity throughout the entire ring. A non-aromatic ring can be a non-aromatic carbocyclic ring, which has only carbon atoms as ring constituent atoms, or a non-aromatic heterocyclic ring, which has heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms. In one embodiment, a non-aromatic carbocyclic ring is preferred. A non-aromatic ring may be a saturated ring or an unsaturated ring. A non-aromatic ring with 3 to 21 members is preferred, a non-aromatic ring with 4 to 17 members is more preferred, and a non-aromatic ring with 5 to 14 members is even more preferred. Suitable examples of non-aromatic rings (non-aromatic carbon rings) include monocyclic non-aromatic saturated carbon rings such as cyclobutane rings, cyclopentane rings, cyclohexane rings, cycloheptane rings, and cyclooctane rings; monocyclic non-aromatic unsaturated carbon rings such as cyclobutene rings, cyclopentene rings, cyclohexene rings, cycloheptene rings, cyclooctene rings, cyclopentadiene rings, and cyclohexadiene rings; bicyclo[2.2.1]heptane rings (norbornane rings), bicyclo[4.4.0]decane rings (decalin rings), bicyclo[5.3.0]decane rings, bicyclo[4.3.0]nonane rings (hydrindane rings), bicyclo[3.2.1]octane rings, bicyclo[5.4.0]undecane rings, bicyclo[3.3.0]octane rings, bicyclo[3.3.1]nonane rings, and tricyclo[5.2.1.0 2,6 ] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7] Decane ring (adamantane ring), tricyclo[6.2.1.0 2,7 Examples of non-aromatic saturated carbocyclic rings with two or more rings, such as undecane rings; bicyclo[2.2.1]hepta-2-ene rings (norbornene rings), bicyclo[2.2.2]octa-2-ene rings, bicyclo[4.4.0]deca-2-ene rings, and other non-aromatic unsaturated carbocyclic rings with two or more rings. Non-aromatic rings may also be non-aromatic rings in which an aromatic ring is partially fused. Examples of non-aromatic rings in which an aromatic ring is partially fused include indane rings, indene rings, tetralin rings, 1,2-dihydronaphthalene rings, 1,4-dihydronaphthalene rings, fluorene rings, 9,10-dihydroanthracene rings, and 9,10-dihydrophenanthrene rings.

[0038] Ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 The "substituents" in the "optionally substituted aromatic ring" and "optionally substituted non-aromatic ring" are not particularly limited, but examples include halogen atoms, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R, -COR, -OR, -SR, -SOR, -SO2R, -NHR, -NR2, -COOR, -OCOR, -CONH2, -CONHR, -CONR2, -NHCOR, etc. (wherein R independently represents a monovalent hydrocarbon group).

[0039] A monovalent hydrocarbon group is a monovalent hydrocarbon group having only one or more (preferably 1 to 50, more preferably 1 to 20) carbon atoms as skeletal atoms and hydrogen atoms as non-skeletal atoms. A monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group. A monovalent hydrocarbon group may or may not have an aromatic structure. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkylaryl groups, and the like.

[0040] An alkyl group refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, alkyl groups having 1 to 14 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, alkyl groups having 1 to 6 carbon atoms are even more preferred, and alkyl groups having 1 to 3 carbon atoms are particularly preferred. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclohexyl, and cyclohexylmethyl groups.

[0041] An alkenyl group refers to a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. Unless otherwise specified, alkenyl groups having 2 to 14 carbon atoms are preferred, alkenyl groups having 2 to 10 carbon atoms are more preferred, alkenyl groups having 2 to 6 carbon atoms are even more preferred, and alkenyl groups having 2 or 3 carbon atoms are particularly preferred. Examples of alkenyl groups include vinyl groups, propenyl groups (allyl group, 1-propenyl group, isopropenyl group), butenyl groups (1-butenyl group, clotyl group, methallyl group, isoclotyl group, etc.), pentenyl groups (1-pentenyl group, etc.), hexenyl groups (1-hexenyl group, etc.), heptenyl groups (1-heptenyl group, etc.), octenyl groups (1-octenyl group, etc.), cyclopentenyl groups (2-cyclopentenyl group, etc.), and cyclohexenyl groups (3-cyclohexenyl group).

[0042] An aryl group refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, aryl groups with 6 to 14 carbon atoms are preferred, and aryl groups with 6 to 10 carbon atoms are more preferred. Examples of aryl groups include phenyl, 1-naphthyl, and 2-naphthyl groups.

[0043] An aralkyl group refers to an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, aralkyl groups having 7 to 15 carbon atoms are preferred, and aralkyl groups having 7 to 11 carbon atoms are more preferred. Examples of aralkyl groups include benzyl, phenethyl, hydrocinnamyl, α-methylbenzyl, α-cumyl, 1-naphthylmethyl, and 2-naphthylmethyl groups.

[0044] The term "alkylaryl group" means an aryl group substituted with one or two or more (preferably one) alkyl groups. Unless otherwise specified, the alkylaryl group is preferably an alkylaryl group having 7 to 15 carbon atoms, more preferably an alkylaryl group having 7 to 11 carbon atoms. Examples of the alkylaryl group include 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-isopropylphenyl group, 3-isopropylphenyl group, 2-isopropylphenyl group, and the like.

[0045] Y 2a , Y 3a , Y 3b , Y 4a , Y 4b , Y 4c , Y 5a , Y 5b , Y 5c and Y 5d each independently represent a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, and in one embodiment, preferably a single bond, -C(R y )2-, or -O-.

[0046] R y each independently represent a hydrogen atom, or an alkyl group optionally substituted with a halogen atom, or two R y bonded together to form a non-aromatic ring optionally having a substituent; in one embodiment, it is preferably a hydrogen atom, or an alkyl group optionally substituted with a halogen atom, more preferably a hydrogen atom, or a methyl group optionally substituted with a halogen atom, still more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

[0047] R yThe "substituents" in the "optionally substituted non-aromatic ring" formed by the compound are not particularly limited, but examples include halogen atoms, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R, -COR, -OR, -SR, -SOR, -SO2R, -NHR, -NR2, -COOR, -OCOR, -CONH2, -CONHR, -CONR2, -NHCOR, etc. (wherein R independently represents a monovalent hydrocarbon group).

[0048] n represents an integer of 0 or greater than or equal to 1; in one embodiment, it is preferably an integer of 0 or between 1 and 10, and more preferably 0.

[0049] Examples of commercially available maleimide resins having a carbon skeleton derived from dimer acid include "BMI-689," "BMI-1500," "BMI-1700," and "BMI-3000J" from Designer Molecules, and "SLK-6895-T90" from Shin-Etsu Chemical Co., Ltd.

[0050] Maleimide resins having a bismaleimide diphenylmethane skeleton are given by formula (2):

[0051] [ka]

[0052] [In the formula, R 10 Each of these independently represents an alkyl group which may be substituted with a hydrogen atom or a halogen atom; Each ring D independently represents an aromatic carbon ring which may have substituents; e represents an integer greater than or equal to 1. It is preferable to include a maleimide compound represented by . The e unit may be the same for each unit or may be different. The maleimide resin having a bismaleimidediphenylmethane skeleton may be used alone or two or more types may be used in any ratio.

[0053] The "substituent" on ring D is not particularly limited, and examples thereof include monovalent substituents such as a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R, -COR, -OR, -SR, -SOR, -SO2R, -NHR, -NR2, -COOR, -OCOR, -CONH2, -CONHR, -CONR2, and -NHCOR (provided that each R independently represents a monovalent hydrocarbon group).

[0054] R 10 each independently represents a hydrogen atom or an alkyl group optionally substituted with a halogen atom; R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

[0055] each ring D independently represents an aromatic ring optionally having a substituent; ring D is preferably a benzene ring optionally having a substituent, more preferably a benzene ring optionally substituted with a group selected from an alkyl group and an aryl group, and particularly preferably an (unsubstituted) benzene ring.

[0056] e represents an integer of 1 or more, and is preferably an integer of 1 to 10.

[0057] Examples of commercially available maleimide resins having a bismaleimide diphenylmethane skeleton include "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd., and the like.

[0058] A maleimide resin having a biphenyl skeleton is represented by formula (3):

[0059] Chemical formula

[0060] [In the formula, R 20 each independently represents a hydrogen atom or an alkyl group optionally substituted with a halogen atom; Rings E, F, and G each independently represent an aromatic carbon ring which may have substituents; f represents an integer greater than or equal to 1. It is preferable to include a maleimide compound represented by . The f units may be the same or different for each unit. The maleimide resin having a biphenyl skeleton may be used alone or two or more may be used in any ratio.

[0061] The "substituents" in rings E, F, and G are not particularly limited, but examples include halogen atoms, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R, -COR, -OR, -SR, -SOR, -SO2R, -NHR, -NR2, -COOR, -OCOR, -CONH2, -CONHR, -CONR2, and -NHCOR (where R independently represents a monovalent hydrocarbon group).

[0062] R 20 Each of these independently represents an alkyl group which may be substituted with a hydrogen atom or a halogen atom, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0063] Rings E, F, and G each independently represent an aromatic ring which may have substituents, preferably an aromatic ring which may have substituents, more preferably an aromatic ring which may be substituted with a group selected from alkyl and aryl groups, and particularly preferably an unsubstituted aromatic ring.

[0064] f represents an integer greater than or equal to 1, preferably an integer between 1 and 10.

[0065] Examples of commercially available maleimide resins containing a biphenyl skeleton include "MIR-3000-70MT" and "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.

[0066] Maleimide resin having an indane skeleton is given by formula (4):

[0067] [ka]

[0068] [In the formula, R 30 Each of these independently represents an alkyl group; Ring H and ring I each independently represent an aromatic carbocyclic ring which may have substituents; m represents an integer greater than or equal to 1. It is preferable that the mixture contains a maleimide resin represented by [formula]. The m units may be the same or different for each unit.

[0069] The "substituents" in ring H and ring I are not particularly limited, but examples include halogen atoms, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R, -COR, -OR, -SR, -SOR, -SO2R, -NHR, -NR2, -COOR, -OCOR, -CONH2, -CONHR, -CONR2, -NHCOR, etc. (where R independently represents a monovalent hydrocarbon group).

[0070] R 30 Each of these independently represents an alkyl group, which in one embodiment is preferably a methyl group.

[0071] Each ring H independently represents an optionally substituted aromatic ring, which in one embodiment is preferably an optionally substituted benzene ring, more preferably an optionally substituted benzene ring with an alkyl group, and even more preferably an alkyl group substituted benzene ring.

[0072] Each ring I independently represents an optionally substituted aromatic ring, which in one embodiment is preferably an optionally substituted benzene ring, more preferably an alkyl-substituted benzene ring, and even more preferably an (unsubstituted) benzene ring.

[0073] m represents an integer greater than or equal to 1, preferably an integer between 1 and 20.

[0074] Maleimide resin having an indan skeleton can be manufactured, for example, by the method described in the Japan Institute of Invention and Innovation Publication No. 2020-500211 or a similar method.

[0075] The maleimide group equivalent of (A) maleimide resin is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, even more preferably 150 g / eq. or more, even more preferably 200 g / eq. or more, even more preferably 250 g / eq. or more, and particularly preferably 300 g / eq. or more, with an upper limit of preferably 2,000 g / eq. or less, more preferably 1,000 g / eq. or less, even more preferably 800 g / eq. or less, even more preferably 600 g / eq. or less, even more preferably 500 g / eq. or less, and particularly preferably 450 g / eq. or less. The maleimide group equivalent is the mass of (A) maleimide resin per molar equivalent of maleimide groups.

[0076] (A) The molecular weight of the maleimide resin is preferably less than 5,000, more preferably less than 3,000, even more preferably less than 2,000, even more preferably less than 1,500, even more preferably less than 1,200, and particularly preferably less than 1,000. The lower limit is not particularly limited, but may be, for example, 300 or more, 400 or more, 500 or more, etc.

[0077] The content of (A) maleimide resin in the resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more, when the total nonvolatile components in the resin composition are taken as 100% by mass. The upper limit is preferably 99% by mass or less, more preferably 90% by mass or less, even more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less.

[0078] (C) When an inorganic filler is included, the content of (A) maleimide resin in the resin composition, when the nonvolatile components excluding (C) the inorganic filler are taken as 100% by mass, is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 8% by mass or more, with an upper limit of preferably 99.9% by mass or less, and particularly preferably 99.5% by mass or less.

[0079] <(B) Salt salts of amine compounds represented by formula (I)> The resin composition of the present invention is (B) Formula (I):

[0080] [ka]

[0081] [In the formula, R 1 , R 2 , R 3 , R 4 and R 5 Each of these independently represents either a hydrogen atom or a substituent. It contains an acid salt of an amine compound represented by (B)(I). The acid salt of the amine compound represented by (B)(I) functions as a maleimide resin curing accelerator, accelerating the curing of the maleimide resin. Furthermore, if an epoxy resin is included, it also functions as an epoxy resin curing accelerator, accelerating the curing of the epoxy resin. The acid salt of the amine compound represented by (B)(I) may be used alone or in combination of two or more types.

[0082] R 1 , R 2 , R 3 , R 4 and R 5 The "substituents" in this context are not particularly limited, but examples include halogen atoms, heteroaryl groups, -CN, -NO2, -OH, -SH, -NH2, -CHO, -R s1 , -OR s1 , -NHR s1 , -N(R s1 )2, -COR s1 ,-COOR s1 , -OCOR s1 , -CONHR s1 , -NHCOR s1 , -SR s1 , -SO2R s1 Examples of monovalent substituents include (where R s1 These are, independently, halogen atoms, heteroaryl groups, -CN, -NO2, -OH, -SH, -NH2, -CHO, -OR s2 , -NHR s2 , -N(R s2 )2, -COR s2 ,-COOR s2 , -OCOR s2 , -CONHR s2 , -NHCOR s2 , -SR s2 , -SO2R s2 This represents a monovalent hydrocarbon group which may be substituted with substituents such as R. s2 Each of these independently represents a monovalent hydrocarbon group.

[0083] A heteroaryl group refers to a monovalent group formed by removing one hydrogen atom from an aromatic heterocycle, which has heteroatoms such as oxygen, nitrogen, and sulfur atoms in addition to carbon atoms as ring constituent atoms. Unless otherwise specified, heteroaryl groups with 5 to 14 members are preferred, and heteroaryl groups with 5 to 10 members are particularly preferred. Examples of heteroaryl groups include furyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, imidazolyl, pyridyl, pyridadinyl, pyrimidinyl, pyrazinyl, and triazinyl groups.

[0084] R 1 and R 5 Each of these independently represents a hydrogen atom or a substituent, and in one embodiment, preferably a hydrogen atom, -OH, -SH, -NH2, -OR s1 , -NHR s1 , -N(R s1 )2, -OCOR s1 , -NHCOR s1 , or -SR s1 (R s1 (As described above), particularly preferably a hydrogen atom.

[0085] R 2 and R 4 Each of these independently represents a hydrogen atom or a substituent, and in one embodiment, it is particularly preferably a hydrogen atom.

[0086] R 3 represents a hydrogen atom or a substituent, which in one embodiment is preferably a substituent, and more preferably -OH, -SH, -NH2, -OR s1 , -NHR s1 , -N(R s1 )2, -OCOR s1 , -NHCOR s1 , or -SR s1 (R s1 (The same as above), more preferably -N(R s1 )2 and (R s1 (As described above), particularly preferably an N,N-dimethylamino group.

[0087] The molecular weight of the amine compound represented by formula (I) is not particularly limited, but is, for example, 4,000 or less, 3,000 or less, 2,000 or less, preferably 1,000 or less, more preferably 700 or less, even more preferably 500 or less, even more preferably 300 or less, even more preferably 200 or less, and particularly preferably 150 or less.

[0088] Specific examples of amine compounds represented by formula (I) include pyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 4-diethylaminopyridine, 2-(aminomethyl)pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-(2-aminoethyl)pyridine, 4-(2-aminoethyl)pyridine, 2-methoxypyridine, 4-methoxypyridine, 2-ethoxypyridine, 4-ethoxypyridine, 2-hydroxypyridine, 4-hydroxypyridine, etc., and among these, 4-dimethylaminopyridine (hereinafter sometimes referred to as "DMAP") is preferred.

[0089] In one embodiment, the salt of the amine compound represented by formula (I) preferably comprises a salt of the amine compound represented by formula (I) and an organic acid selected from carboxylic acids (including aliphatic carboxylic acids and aromatic carboxylic acids) and sulfonic acids (including aliphatic sulfonic acids and aromatic sulfonic acids); more preferably, a salt of the amine compound represented by formula (I) and formulas (IIa) to (IIc):

[0090] [ka]

[0091] [In the formula, X represents -CO- or -SO2-; R a , R b , Rc , R d , R e , R f and R g Each of these independently represents either a hydrogen atom or a substituent. It contains a salt with an organic acid represented by one of the following.

[0092] R a , R b , R c , R d , R e , R f and R g The "substituents" in this context are not particularly limited, but examples include halogen atoms, heteroaryl groups, -CN, -NO2, -OH, -SH, -CHO, -COOH, -SO3H, -R t1 , -OR t1 , -COR t1 ,-COOR t1 , -OCOR t1 , -CONHR t1 , -NHCOR t1 , -SR t1 , -SO2R t1 Examples of monovalent substituents include (where R t1 These are, independently, halogen atoms, heteroaryl groups, -CN, -NO2, -OH, -SH, -CHO, -COOH, -SO3H, -OR t2 , -COR t2 ,-COOR t2 , -OCOR t2 , -CONHR t2 , -NHCOR t2 , -SR t2 , -SO2R t2 This represents a monovalent hydrocarbon group which may be substituted with substituents such as R. t2 Each of these independently represents a monovalent hydrocarbon group.

[0093] R a , R b , R c , R d , R e , R f and R gEach of these independently represents a hydrogen atom or a substituent, and in one embodiment, preferably a hydrogen atom, -COOH, -SO3H, or -R t1 The most common members are a hydrogen atom, a methyl group, -COOH, or -SO3H.

[0094] The molecular weight of the organic acid represented by any of formulas (IIa) to (IIc) is not particularly limited, but for example it is 4,000 or less, 3,000 or less, or 2,000 or less, preferably 1,000 or less, more preferably 700 or less, even more preferably 500 or less, even more preferably 400 or less, even more preferably 300 or less, and particularly preferably 250 or less.

[0095] A specific example of an organic acid represented by any of formulas (IIa) to (IIc) is benzoic acid (pK a =4.2), o-toluic acid (pK a =3.9), m-toluic acid (pK a =4.3), p-toluic acid (pK a =4.4), 2-ethylbenzoic acid (pK a =3.8), 3-ethylbenzoic acid (pK a =4.3), 4-ethylbenzoic acid (pK a =4.4), 2-isopropylbenzoic acid (pK a =3.6), 2-tert-butylbenzoic acid (pK a =3.5), 2,3-dimethylbenzoic acid (pK a =3.8), 2,4-dimethylbenzoic acid (pK a =4.2), 2,5-dimethylbenzoic acid (pK a =4.0), 2,6-dimethylbenzoic acid (pK a =3.4), 3,5-dimethylbenzoic acid (pK a =4.3), 2,4,6-trimethylbenzoic acid (pK a =3.4), 2,4,6-triisopropylbenzoic acid (pK a =3.2), o-anisic acid (pK a =4.1), m-anisic acid (pK a =4.1), p-anisic acid (pK a=4.5), 2,6-dimethoxybenzoic acid (pK a =3.4), 2-ethoxybenzoic acid (pK a =4.2), 2-acetamidobenzoic acid (pK a =3.6), 2-acetoxybenzoic acid (pK a =4.6), 2-acetylbenzoic acid (pK a =4.1), 3-acetylbenzoic acid (pK a =3.8), 2-phenylbenzoic acid (pK a =3.5), 3-phenylbenzoic acid (pK a =4.1), 4-phenylbenzoic acid (pK a =4.2), 2-phenoxybenzoic acid (pK a =3.5), 2-benzoylbenzoic acid (pK a =3.5), 2-fluorobenzoic acid (pK a =3.3), 3-fluorobenzoic acid (pK a =3.9), 4-fluorobenzoic acid (pK a =4.2), pentafluorobenzoic acid (pK a =1.8), 2-chlorobenzoic acid (pK a =2.9), 2,4-dichlorobenzoic acid (pK a =2.7), 2,5-dichlorobenzoic acid (pK a =2.5), 2,6-dichlorobenzoic acid (pK a =1.6), 2-bromobenzoic acid (pK a =2.8), 2-nitrobenzoic acid (pK a =2.2), 3-nitrobenzoic acid (pK a =3.5), 4-nitrobenzoic acid (pK a =3.4), 2-cyanobenzoic acid (pK a =3.1), 2-hydroxybenzoic acid (pK a =3.0), 4-(trifluoromethyl)benzoic acid (pK a =3.7), 2,6-bis(trifluoromethyl)benzoic acid (pK a =2.3), 1-Naphthoic acid (pK a =3.7), 2-naphthoic acid (pK a Aromatic monocarboxylic acids such as (=4.2); phthalic acid (pK a1=2.9), isophthalic acid (pK a1 =3.5), terephthalic acid (pK a1 =3.5), 4-methylphthalic acid (pK a1 =3.3), 5-methylisophthalic acid (pK a1 =3.6), 5-methylterephthalic acid (pK a1 =3.4), 3-methoxyphthalic acid (pK a1 =3.1), 4-methoxyphthalic acid (pK a1 =3.1), 3-fluorophthalic acid (pK a1 =2.3), 4-fluorophthalic acid (pK a1 =2.9), tetrafluorophthalic acid (pK a1 =1.3), 1,4-naphthalenedicarboxylic acid (pK a1 =2.7), 2,3-naphthalenedicarboxylic acid (pK a1 =3.0), 2,6-naphthalenedicarboxylic acid (pK a1 =3.7), 2,7-naphthalenedicarboxylic acid (pK a1 =3.7), hemimeric acid (pK a1 =2.9), trimellitic acid (pK a1 =2.5), trimesic acid (pK a1 =3.1), pyromellitic acid (pK a1 Aromatic polycarboxylic acids such as (=1.9); benzenesulfonic acid (pK a =-2.8), p-toluenesulfonic acid (pK a =-2.8), p-xylene-2-sulfonic acid (pK a =-0.5), naphthalene sulfonic acid (pK a Aromatic monovalent sulfonic acids such as (=0.3); 1,3-benzenedisulfonic acid (pK a1 =-1.4), 1,2-benzenedisulfonic acid (pK a1 =-1.1), 1,3,5-benzenetrisulfonic acid (pK a1 Examples include aromatic polyvalent sulfonic acids such as (-2.1), and among these, organic acids selected from phthalic acid, trimellitic acid, and p-toluenesulfonic acid are preferred.

[0096] In one embodiment, the salt of the amine compound represented by formula (I) is preferably an amine compound represented by formula (I) and an acid dissociation constant (pK) in water at 25°C. a A salt with an organic acid (preferably a carboxylic acid or sulfonic acid, especially preferably an organic acid represented by any of formulas (IIa) to (IIc)) having an acid dissociation constant (pK) of 4.5 or less, more preferably an organic acid with an acid dissociation constant (pK) of 4.5 or less in water at 25°C. a A salt of an organic acid (preferably a carboxylic acid or sulfonic acid, especially preferably an organic acid represented by any of formulas (IIa) to (IIc)) with an acid dissociation constant (pK) of 4.0 or less in water at 25°C, more preferably an acid dissociation constant (pK) of 4.0 or less in water, and more preferably an acid dissociation constant (pK) of 4.0 or less in water at 25°C. a A salt with an organic acid (preferably a carboxylic acid or sulfonic acid, especially preferably an organic acid represented by any of formulas (IIa) to (IIc)) having an acid dissociation constant (pK) of 3.5 or less, and more preferably an acid dissociation constant (pK) of water at 25°C. a The salt includes an organic acid with a dissociation constant (pK) of 3.0 or less (preferably a carboxylic acid or sulfonic acid, and especially preferably an organic acid represented by any of formulas (IIa) to (IIc)). Here, the acid dissociation constant is the lowest acid dissociation constant (pK) of the first step in the case of a polyhydric organic acid. a1 ) means.

[0097] The content of the salt of the amine compound represented by formula (I) in the resin composition is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, when the total nonvolatile components in the resin composition are taken as 100% by mass. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0098] (C) When an inorganic filler is included, the content of the salt of the amine compound represented by formula (I) (B), when the nonvolatile components excluding the inorganic filler in the resin composition are taken as 100% by mass, is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more, with an upper limit of preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0099] The mass ratio of (B) salt of the amine compound represented by formula (I) to (A) maleimide resin in the resin composition (content of component (B) / content of component (A)) is preferably 0.00001 or more, more preferably 0.0001 or more, even more preferably 0.001 or more, and particularly preferably 0.005 or more, with an upper limit of preferably 0.3 or less, more preferably 0.2 or less, even more preferably 0.15 or less, and particularly preferably 0.1 or less.

[0100] <(C) Inorganic filler> The resin composition of the present invention may further contain (C) an inorganic filler as an optional component. (C) The inorganic filler is included in the resin composition in the form of particles.

[0101] (C) Inorganic compounds are used as the material for the inorganic filler. (C) Examples of materials for the inorganic filler include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica, alumina, or aluminosilicate are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred as the silica. (C) Inorganic fillers may be used individually or in combination of two or more types in any ratio.

[0102] (C) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" from Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" from Admatex Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" from Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; "Cellspheres" and "MGH-005" from Taiheiyo Cement Corporation; "Esferique" and "BA-1" from JGC Catalysts & Chemicals Co., Ltd.; and "Highpresica FH" from Ube Eximo Co., Ltd.

[0103] (C) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, even more preferably 1 μm or less, and particularly preferably 0.8 μm or less. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (C) The average particle size of the inorganic filler can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the median diameter can be used as the average particle size. A sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them with ultrasound for 10 minutes. The particle size distribution of the inorganic filler was measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths, employing a flow cell method. The average particle size was calculated as the median diameter from the obtained particle size distribution. Examples of laser diffraction particle size distribution analyzers include the "LA-960" manufactured by Horiba, Ltd.

[0104] (C) The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m². 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 (C) The upper limit of the specific surface area of ​​the inorganic filler is not particularly limited, but preferably 100 m². 2 / g or less, more preferably 50m 2 / g or less, more preferably 30m 2 / g or less, particularly preferably 10m 2 The value is less than / g. The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0105] (C) The inorganic filler may be a solid inorganic filler with an average porosity of 0 volume% (preferably solid silica, solid alumina, or solid aluminosilicate), or a hollow inorganic filler with an average porosity of more than 0 volume% (preferably hollow silica, hollow alumina, or hollow aluminosilicate).

[0106] (C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. Furthermore, the surface treatment agent may be used alone or in any combination of two or more types.

[0107] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane), "KBM-4803" (long-chain epoxy-type silane coupling agent), and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), all manufactured by Shin-Etsu Chemical Co., Ltd.

[0108] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably with 0.2% to 3% by mass, and even more preferably with 0.3% to 2% by mass.

[0109] The degree of surface treatment by a 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 should be 0.02 mg / m². 2 The above is preferred, and 0.1 mg / m² 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in sheet form, 1.0 mg / m² 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2 The following are even more preferable.

[0110] (C) The amount of carbon per unit surface area of ​​an inorganic filler can be measured after cleaning the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) following surface treatment. Specifically, a sufficient amount of MEK is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0111] The content of (C) inorganic filler in the resin composition is, for example, 0% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, with an upper limit of preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, and particularly preferably 80% by mass or less.

[0112] The mass ratio of (C) inorganic filler to (A) maleimide resin in the resin composition (component (C) / component (A)) is not particularly limited, but is, for example, 0 or more, preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, even more preferably 0.7 or more, even more preferably 1.0 or more, and particularly preferably 1.3 or more, with an upper limit of preferably 200 or less, more preferably 100 or less, even more preferably 50 or less, and particularly preferably 30 or less.

[0113] The total content of (A) maleimide resin, (B) an acid salt of an amine compound represented by formula (I), and (C) an inorganic filler in the resin composition is, for example, 5% by mass or more, 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 74% by mass or more, when the total nonvolatile components in the resin composition are taken as 100% by mass.

[0114] <(D) Anionic polymerizing curing agent> The resin composition of the present invention may further contain (D) an anionic polymerizable curing agent as an optional component. The (D) anionic polymerizable curing agent may have the function of curing maleimide resins, epoxy resins, etc., by anionic reaction. The (D) anionic polymerizable curing agent may be used alone or two or more types may be used in any combination.

[0115] (D) Examples of anionic polymerizable curing agents include phenolic curing agents, carbodiimide curing agents, amine curing agents, benzoxazine curing agents, and active ester curing agents. (D) Among these, it is preferable that the anionic polymerizable curing agent includes a phenolic curing agent.

[0116] As phenolic curing agents, curing agents having one or more, preferably two or more, hydroxyl groups (phenolic hydroxyl groups) bonded to aromatic rings such as benzene rings and naphthalene rings in one molecule can be used. Examples of phenolic curing agents include phenolic curing agents having a polyphenylene ether structure, phenolic curing agents having a biphenyl structure (particularly preferably containing a 1-propenyl group), and phenolic curing agents having a novolac structure (particularly preferably containing a triazine skeleton). These may be used individually or in combination of two or more types.

[0117] Examples of commercially available phenolic curing agents include "MEH-7700," "MEH-7810," and "MEH-7851" from Meiwa Kasei Co., Ltd.; "NHN," "CBN," and "GPH" from Nippon Kayaku Co., Ltd.; "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-375," and "SN-395" from Nippon Steel Chemical & Material Co., Ltd.; "LA-7052," "LA-7054," "LA-3018," "LA-3018-50P," "LA-1356," "TD-2090," "TD-2090-60M," and "KA-1160" from DIC Corporation; and "SA90" from SABIC Corporation. These may be used individually or in combination of two or more types.

[0118] Examples of carbodiimide-based curing agents include curing agents having one or more, preferably two or more, carbodiimide structures in one molecule, such as aliphatic biscarbodiimides like tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides like aromatic biscarbodiimides like phenylene-bis(xylylcarbodiimide); and aliphatic polycarbodiimides like polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(trylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. These may be used individually or in combination of two or more types.

[0119] Examples of commercially available carbodiimide-based curing agents include "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" from Nisshinbo Chemical Co., Ltd., and "Stabaczol P," "Stabaczol P400," and "Hycazil 510" from Rhein Chemie Corporation. These may be used individually or in combination of two or more types.

[0120] Examples of amine-based curing agents include curing agents having one or more, preferably two or more, amino groups in one molecule. Examples include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and among these, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine.

[0121] Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl) Examples include propyl propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Commercially available amine-based curing agents may be used, such as "SEIKACURE-S" from Seika Corporation; "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" from Nippon Kayaku Co., Ltd.; "Epicure W" from Mitsubishi Chemical Corporation; "DTDA" from Sumitomo Seika Co., Ltd.; and "WA" from DIC Corporation. These may be used individually or in combination of two or more types.

[0122] Examples of benzoxazine-based curing agents include curing agents having one or more, preferably two or more, benzoxazine structures within a single molecule.

[0123] Commercially available benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" from JFE Chemical Corporation; "HFB2006M" from Showa Polymer Co., Ltd.; and "Pd," "Fa," and "ALP-d" from Shikoku Chemicals Co., Ltd. These may be used individually or in combination of two or more types.

[0124] As active ester curing agents, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are generally preferred. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and / or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two phenol molecules with one dicyclopentadiene molecule.

[0125] As active ester curing agents, specifically, dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac resin, and active ester compounds containing a benzoylated phenol novolac resin are preferred, and more preferably, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds. As dicyclopentadiene-type active ester compounds, active ester compounds containing a dicyclopentadiene-type diphenol structure are preferred.

[0126] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation); and active ester compounds containing a naphthalene structure such as "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "HPC-8150-62T", and "EX Examples of phosphorus-containing active ester compounds include "EXB9401" (manufactured by DIC Corporation), "DC808" (manufactured by Mitsubishi Chemical Corporation) as an acetylated active ester compound of phenol novolac resin, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as benzoylated active ester compounds of phenol novolac resin, and "PC1300-02-65MA" (manufactured by Air Water Corporation) as an active ester compound containing a vinylphenyl group and a naphthalene structure.

[0127] (D) The reactive group equivalent of the anionic polymerizable curing agent is preferably 3,000 g / eq. or less, more preferably 2,000 g / eq. or less, even more preferably 1,000 g / eq. or less, and particularly preferably 800 g / eq. or less, with a lower limit of preferably 40 g / eq. or more, more preferably 60 g / eq. or more, even more preferably 80 g / eq. or more, and particularly preferably 100 g / eq. or more. The reactive group equivalent is the mass of (D) anionic polymerizable curing agent per molar equivalent of reactive group. A reactive group refers to a functional group that reacts anionically with maleimide resin, epoxy resin, etc. For example, in the case of a phenolic curing agent, it refers to a phenolic hydroxyl group; in the case of a carbodiimide curing agent, it refers to a carbodiimide group (-N=C=N-); in the case of an amine curing agent, it refers to an amino group; in the case of a benzoxazine curing agent, it refers to a benzoxazinyl group; and in the case of an active ester curing agent, it refers to a reactive ester group (ester of a phenolic hydroxyl group).

[0128] The content of (D) anionic polymerizable curing agent in the resin composition is, for example, 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, and particularly preferably 1% by mass or more, when the total nonvolatile components in the resin composition are taken as 100% by mass. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0129] (C) When an inorganic filler is included, the content of (D) anionic polymerizable curing agent, when the nonvolatile components excluding (C) the inorganic filler in the resin composition are taken as 100% by mass, is, for example, 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 3% by mass or more, with an upper limit of preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

[0130] The mass ratio of (D) anionic polymerizable curing agent to (A) maleimide resin in the resin composition (content of (D) / content of (A)) is, for example, 0 or more, preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.03 or more, and particularly preferably 0.05 or more, with an upper limit of preferably 20 or less, more preferably 10 or less, even more preferably 7 or less, and particularly preferably 5 or less.

[0131] <(E) Epoxy resin> The resin composition of the present invention may further contain (E) epoxy resin as an optional component. (E) epoxy resin is a curable resin having epoxy groups and an epoxy equivalent of 5,000 g / eq. or less.

[0132] (E) Examples of epoxy resins include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiroring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthaleimidine type epoxy resin, and the like. (E) Epoxy resin may be used alone or in combination of two or more types.

[0133] The resin composition of the present invention preferably contains an epoxy resin having two or more epoxy groups in one molecule as (E) epoxy resin. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of (E) epoxy resin.

[0134] (E) Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only liquid epoxy resin, or only solid epoxy resin, or both liquid epoxy resin and solid epoxy resin, but it is particularly preferable to contain both liquid epoxy resin and solid epoxy resin.

[0135] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0136] Preferred liquid epoxy resins include glycirol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, glycidyl ester-type epoxy resins, glycidylamine-type epoxy resins, phenol novolac-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cyclic aliphatic glycidyl ethers, and epoxy resins having a butadiene structure.

[0137] Specific examples of liquid epoxy resins include "EX-992L" from Nagase ChemteX, "YX7400" from Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) from DIC Corporation; "828US", "jER828EL", "828EL", "825", and "Epicote 828EL" (bisphenol A-type epoxy resin) from Mitsubishi Chemical Corporation; and "jER807" and "1750" from Mitsubishi Chemical Corporation. Bisphenol F type epoxy resin; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycyrol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "EX-991L" (epoxy resin containing alkylene oxy skeleton and butadiene skeleton) manufactured by Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation Examples include "PB-3600" from Daicel Corporation, "JP-100" and "JP-200" from Nippon Soda Co., Ltd. (epoxy resins with a butadiene structure); "ZX1658" and "ZX1658GS" from Nippon Steel Chemical & Material Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resins); "EG-280" from Osaka Gas Chemical Co., Ltd. (fluorene structure-containing epoxy resin); and "EX-201" from Nagase ChemteX Corporation (cyclic aliphatic glycidyl ether).

[0138] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is more preferred.

[0139] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolac-type epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, phenol aralkyl-type epoxy resin, tetraphenylethane-type epoxy resin, and phenolphthaleimidine-type epoxy resin.

[0140] Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol novolac-type epoxy resin); DIC's "N-695" (cresol novolac-type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resins); DIC's "EXA-7311" and "E XA-7311-G3, EXA-7311-G4, EXA-7311-G4S, HP6000, HP6000L (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin); Nippon Steel Chemical & Material Co., Ltd.'s "ESN475V", "ESN4100V" (naphthalene-type epoxy resin); "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Examples include "YX7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) from Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) from Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) from Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) from Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalein-imidine type epoxy resin) from Nippon Kayaku Co., Ltd.These may be used individually or in combination of two or more types.

[0141] (E) When using a combination of liquid epoxy resin and solid epoxy resin as the epoxy resin, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 10:1 to 1:50, more preferably 5:1 to 1:20, even more preferably 2:1 to 1:10, and particularly preferably 1:1 to 1:3.

[0142] (E) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0143] (E) The weight-average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight-average molecular weight of the resin can be measured as a polystyrene equivalent by gel permeation chromatography (GPC).

[0144] The content of (E) epoxy resin in the resin composition is, for example, 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more, when the total nonvolatile components in the resin composition are taken as 100% by mass. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0145] (C) When an inorganic filler is included, the content of (E) epoxy resin when the nonvolatile components excluding the (C) inorganic filler in the resin composition are set to 100% by mass is, for example, 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more, with an upper limit of preferably 90% by mass or less, more preferably 75% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

[0146] The mass ratio of (E) epoxy resin to (A) maleimide resin in the resin composition (content of (E) / content of (A)) is, for example, 0 or more, preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.05 or more, and particularly preferably 0.1 or more, with an upper limit of preferably 20 or less, more preferably 10 or less, even more preferably 7 or less, and particularly preferably 5 or less.

[0147] <(F)Thermoplastic resin> The resin composition of the present invention may further contain (F) a thermoplastic resin as an optional component. The (F) thermoplastic resin described herein is a component other than the (D) anionic polymerizable curing agent and (E) epoxy resin described above.

[0148] (F) Examples of thermoplastic resins include polystyrene resin, oxazoline group-containing resin, polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. (F) In one embodiment, the thermoplastic resin preferably includes a thermoplastic resin selected from the group consisting of polystyrene resin, oxazoline group-containing resin, polyimide resin, and phenoxy resin, more preferably includes a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and particularly preferably includes a phenoxy resin. Furthermore, the thermoplastic resin may be used alone or in combination of two or more types.

[0149] The polystyrene resin may be a commercially available product, for example, hydrogenated styrene thermoplastic elastomers "H1041", "ToughTec H1043", "ToughTec P2000", "ToughTec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT501", "CT310" (manufactured by Daicel Corporation); modified styrene elastomer with hydroxyl groups "Septon HG252" (manufactured by Kuraray Co., Ltd.); modified styrene elastomer with carboxyl groups "ToughTec N503M", modified styrene elastomer with amino groups "ToughTec N501", modified styrene elastomer with acid anhydride groups "ToughTec M1913" (manufactured by Asahi Kasei Chemicals Corporation); unmodified styrene elastomer "Septon S8104" (manufactured by Kuraray Co., Ltd.).

[0150] Oxazoline group-containing resins include, for example, 2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 4,4,5-trimethyl-2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, and 4-methyl-2-vinyl These resins are obtained by polymerizing addition-polymerizable oxazoline compounds (vinyl oxazoline skeleton-containing monomers) such as nyl-2-oxazoline and 4,4,5-trimethyl-2-vinyl-2-oxazoline, and may optionally be copolymerized with other monomers such as styrene, α-methylstyrene, 4-methylstyrene, 3-methylstyrene, 2-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, p-divinylbenzene, and m-divinylbenzene. Specific examples of oxazoline group-containing resins include "PX-3-RP-61" manufactured by Nippon Shokubai Co., Ltd.

[0151] Specific examples of polyimide resins include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., and "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin-Nippon Rika Co., Ltd.

[0152] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal end of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0153] Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation; "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0154] Examples of polyvinyl acetal resins include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" from Denki Kagaku Kogyo Co., Ltd.; and S-Rec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series from Sekisui Chemical Co., Ltd.

[0155] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0156] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0157] Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Other specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Co., Ltd.

[0158] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0159] Specific examples of polysulfone resins include Solvay Advanced Polymers' polysulfones "P1700" and "P3500".

[0160] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resins include "Ultem" manufactured by GE.

[0161] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" from Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) from Asahi Kasei Chemicals Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) from Kuraray Co., Ltd. Specific examples of polyether ether ketone resins include "Sumiproi K" from Sumitomo Chemical Co., Ltd.

[0162] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin.

[0163] (F) The weight-average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less, from the viewpoint of significantly obtaining the effects of the present invention.

[0164] The content of (F) thermoplastic resin in the resin composition is, for example, 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more, when the total nonvolatile components in the resin composition are taken as 100% by mass. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0165] When the resin composition contains (C) an inorganic filler, the content of (F) a thermoplastic resin, based on 100% by mass of non-volatile components excluding (C) the inorganic filler in the resin composition, is, for example, 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 8% by mass or more, and the upper limit thereof is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0166] The mass ratio of (F) the thermoplastic resin to (A) the maleimide resin in the resin composition (content of component (F) / content of component (A)) is, for example, 0 or more, preferably 0.001 or more, more preferably 0.01 or more, still more preferably 0.1 or more, and particularly preferably 0.3 or more, and the upper limit thereof is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, even more preferably 2 or less, and particularly preferably 1.5 or less.

[0167] The total content of (A) the maleimide resin, (B) an acid salt of an amine compound represented by formula (I), (C) the inorganic filler, (D) an anion polymerizable curing agent, (E) an epoxy resin, and (F) the thermoplastic resin in the resin composition is not particularly limited, but when all non-volatile components in the resin composition are taken as 100% by mass, it is, for example, 30% by mass or more, 50% by mass or more, 70% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, still further more preferably 98% by mass or more, and particularly preferably 99% by mass or more.

[0168] <(G) Radical polymerization initiator> The resin composition of the present invention may further contain (G) a radical polymerization initiator as an optional component. The (G) radical polymerization initiator is preferably, for example, a thermal polymerization initiator that generates free radicals when heated. The (G) radical polymerization initiator may be used alone or in any combination of two or more types.

[0169] (G) Examples of radical polymerization initiators include peroxide-based radical polymerization initiators and azo-based radical polymerization initiators. Among these, peroxide-based radical polymerization initiators are preferred.

[0170] Examples of peroxide-based radical polymerization initiators include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkylperoxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; and diacylperoxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl) peroxydicarbonate. Examples of peroxyester compounds include tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)2-ethyl perhexanoate, tert-butyl 2-ethyl perhexanoate, tert-butyl 3,5,5-trimethyl perhexanoate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxymaleic acid, and others.

[0171] Examples of azo radical polymerization initiators include azonitrile compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitride), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide], and 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide]. Examples include azoamide compounds such as methyl)ethyl[propionamide], 2,2'-azobis[2-methyl-N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(2-methylpropionamide) dihydrate, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); and alkylazo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane).

[0172] (G) Examples of commercially available radical polymerization initiators include NOF Corporation's "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", "Perbutyl ND", "Perbutyl Z", "Perbutyl I", "Permil P", "Permil D", "Perhexyl D", "Perhexyl A", "Perhexyl I", "Perhexyl Z", "Perhexyl ND", "Perhexyl O", and "Perhexyl PV".

[0173] The content of (G) radical polymerization initiator in the resin composition is not particularly limited, but when the nonvolatile components in the resin composition are taken as 100% by mass, it is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.7% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit is not particularly limited, but when the nonvolatile components in the resin composition are taken as 100% by mass, it may be, for example, 0% by mass or more, 0.0001% by mass or more, preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more.

[0174] <(H) Other additives> The resin composition of the present invention may further contain any additives. Such additives include, for example, curing accelerators other than salts of amine compounds represented by formula (I), such as phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators; radical polymerizable compounds having allyl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, etc.; organic fillers such as rubber particles; organometallic compounds such as organocuone compounds, organozinc compounds, and organocuone compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; defoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; and benzotriazole Examples of adhesives include: UV absorbers such as oleopropyl UV absorbers; adhesion improvers such as urea silane; adhesion fertilizers such as triazole-based adhesion fertilizers, tetrazole-based adhesion fertilizers, and triazine-based adhesion fertilizers; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. (H) Other additives may be used individually or in combination of two or more in any ratio. (H) The content of other additives can be appropriately determined by a person skilled in the art.

[0175] <(I) Organic Solvents> The resin composition of the present invention may further contain any organic solvent. (I) Known organic solvents can be used as appropriate, and the type is not particularly limited. (I) Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methoxypropionic acid Examples include ether ester solvents such as methyl; 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. (I) Organic solvents may be used individually or in combination of two or more in any ratio.

[0176] The content of (I) organic solvent in the varnish-like resin composition before drying is not particularly limited, but when the total components in the resin composition are considered as 100% by mass, for example, it is 40% by mass or less, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less. The content of (I) organic solvent in the dried resin composition that forms the resin composition layer in the resin sheet is not particularly limited, but when the total components in the resin composition are considered as 100% by mass, it is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0177] <Method for producing resin compositions> The resin composition of the present invention can be produced, for example, by adding (A) maleimide resin, (B) an acid salt of an amine compound represented by formula (I), optionally (C) an inorganic filler, optionally (D) an anionic polymerizable curing agent, optionally (E) an epoxy resin, optionally (F) a thermoplastic resin, and optionally (G) a radical polymerization initiator to any preparation container and mixing them in any order and / or partially or entirely simultaneously. Furthermore, the temperature can be set appropriately during the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout the process. In addition, during or after the process of adding and mixing, the resin composition may be stirred or shaken using, for example, a stirring device such as a mixer or a shaking device to disperse it uniformly. Furthermore, degassing may be performed simultaneously with stirring or shaking under low pressure conditions such as vacuum.

[0178] <Properties of resin compositions> The resin composition of the present invention comprises (A) a maleimide resin and (B) an acid salt of an amine compound represented by formula (I). With such a resin composition, it is possible to obtain a cured product that maintains excellent copper foil adhesion strength even after accelerated environmental testing (HAST) and has a high glass transition temperature.

[0179] The cured product of the resin composition of the present invention has a high glass transition temperature (Tg). Therefore, for example, the glass transition temperature (Tg) measured as in Test Example 1 below can be preferably 100°C or higher, more preferably 120°C or higher, even more preferably 130°C or higher, even more preferably 140°C or higher, even more preferably 145°C or higher, and particularly preferably 150°C or higher.

[0180] The cured resin composition of the present invention is characterized by high copper foil adhesion strength (copper foil peel strength) after accelerated environmental testing (HAST). Therefore, as shown in Test Example 2 below, the copper foil adhesion strength (copper foil peel strength) after accelerated environmental testing (HAST), measured in accordance with JIS C6481, is preferably 0.1 kgf / cm or more, more preferably 0.2 kgf / cm or more, even more preferably 0.3 kgf / cm or more, even more preferably 0.35 kgf / cm or more, and particularly preferably 0.4 kgf / cm or more. Similarly, the copper foil adhesion strength (copper foil peel strength) before accelerated environmental testing (HAST), measured before the same test, is preferably 0.1 kgf / cm or more, more preferably 0.2 kgf / cm or more, even more preferably 0.4 kgf / cm or more, even more preferably 0.5 kgf / cm or more, even more preferably 0.6 kgf / cm or more, and particularly preferably 0.65 kgf / cm or more. Furthermore, the percentage decrease in copper foil adhesion strength after the accelerated environmental test (HAST) compared to the copper foil adhesion strength before the HAST test [(1 - copper foil adhesion strength after HAST / copper foil adhesion strength before HAST) × 100 (%)] is preferably 80% or less, more preferably 70% or less, even more preferably 60% or less, even more preferably 55% or less, and particularly preferably 50% or less.

[0181] <Uses of resin compositions> The resin composition of the present invention can be suitably used as a resin composition for insulating applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming the insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer (resin composition for forming an insulating layer for forming a conductor layer). It can also be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board) in the printed wiring board described later. The resin composition of the present invention can also be widely used in applications where a resin composition is required, such as sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulating materials, hole-filling resins, and component-embedding resins.

[0182] 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 be suitably used also as a resin composition for a rewiring formation layer serving as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer) and a resin composition for encapsulating a semiconductor chip (resin composition for semiconductor chip encapsulation). When manufacturing a semiconductor chip package, an additional rewiring layer may be formed on the encapsulating layer. (1) a step of laminating a temporary fixing film on a base material, (2) a step of temporarily fixing a semiconductor chip on the temporary fixing film, (3) a step of forming an encapsulating layer on the semiconductor chip, (4) a step of peeling the base material and the temporary fixing film from the semiconductor chip, (5) a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled, and (6) a step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0183] Furthermore, since the resin composition of the present invention provides an insulating layer with excellent component embedding properties, it can also be suitably used when the printed wiring board is a component-embedded circuit board.

[0184] <Sheet-like laminated material> The resin composition of the present invention can be used by applying it in a varnish state, but industrially it is generally preferable to use it in the form of a sheet-like laminate material containing the resin composition.

[0185] As sheet-like laminated materials, the following resin sheets and prepregs are preferred.

[0186] In one embodiment, the resin sheet comprises a support and a resin composition layer provided on the support, the resin composition layer being formed from the resin composition of the present invention.

[0187] The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of thinning the printed circuit board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more, 10 μm or more, etc.

[0188] Examples of support materials include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

[0189] When using a film made of plastic material as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0190] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As for copper foil, foil made of single-metal copper may be used, or foil made of an alloy of copper with another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0191] The support may have a matte finish, corona treatment, or antistatic treatment applied to the surface that bonds with the resin composition layer.

[0192] Furthermore, as the support, a support with a release layer may be used, which has a release layer on the surface that is bonded to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may be used as the support with a release layer, for example, PET films having a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1", "AL-5", and "AL-7" from Lintec Corporation, "Lumirror T60" from Toray Industries, Inc., "Purex" from Teijin Corporation, and "Unipeel" from Unitika Corporation.

[0193] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When using a support with a release layer, it is preferable that the overall thickness of the support with the release layer is within the above range.

[0194] In one embodiment, the resin sheet may further include any additional layer as needed. Such an additional layer may be, for example, a protective film similar to the support, provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of dust and other debris to the surface of the resin composition layer and scratches can be suppressed.

[0195] Resin sheets can be manufactured, for example, by using a liquid (varnish-like) resin composition as is, or by preparing a liquid (varnish-like) resin composition by dissolving the resin composition in an organic solvent, applying this to a support using a die coater or the like, and then drying it to form a resin composition layer.

[0196] Examples of organic solvents include those similar to those described as components of the resin composition. Organic solvents may be used individually or in combination of two or more.

[0197] Drying may be carried out by known methods such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer should be dried 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. Depending on the boiling point of the organic solvent in the resin composition, for example, when using a resin composition containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0198] The resin sheet can be stored by rolling it up. If the resin sheet has a protective film, it can be used after removing the protective film.

[0199] In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous substrate with the resin composition of the present invention.

[0200] The sheet-like fibrous substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed circuit board, the thickness of the sheet-like fibrous substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous substrate is not particularly limited, but is usually 10 μm or more.

[0201] Prepregs can be manufactured by known methods such as the hot melt method and the solvent method.

[0202] The thickness of the prepreg can be within the same range as the resin composition layer in the resin sheet described above.

[0203] The sheet-like laminated material of the present invention can be suitably used to form an insulating layer of a printed circuit board (for the insulating layer of a printed circuit board), and more suitably used to form an interlayer insulating layer of a printed circuit board (for the interlayer insulating layer of a printed circuit board).

[0204] <Printed wiring board> The printed circuit board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0205] Printed circuit boards can be manufactured, for example, using the resin sheet described above, by a method including the following steps (I) and (II). (I) A process of laminating a resin sheet onto an inner layer substrate such that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., thermal curing) the resin composition layer to form an insulating layer.

[0206] The "internal layer substrate" used in process (I) is a material that serves as the substrate for a printed wiring board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. The substrate may also have a conductive layer on one or both sides, and this conductive layer may be patterned. An internal layer substrate in which a conductive layer (circuit) is formed on one or both sides of the substrate is sometimes called an "internal layer circuit board." Furthermore, an intermediate product on which an insulating layer and / or a conductive layer is to be formed during the manufacturing of a printed wiring board is also included in the "internal layer substrate" as defined in this invention. If the printed wiring board is a circuit board with embedded components, an internal layer substrate with embedded components may be used.

[0207] Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet onto the inner layer substrate from the support side. Examples of the member used to heat and press the resin sheet onto the inner layer substrate (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS end plate) or a metal roll (such as a SUS roll). It is preferable to press the resin sheet via an elastic material such as heat-resistant rubber, rather than directly pressing the heat-pressing member onto the resin sheet, so that the resin sheet can adequately follow the surface irregularities of the inner layer substrate.

[0208] Lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the heat-pressure temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressure pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat-pressure time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination may preferably be carried out under reduced pressure conditions of 26.7 hPa or less.

[0209] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch-type vacuum pressure laminators.

[0210] After lamination, the laminated resin sheets may be smoothed by pressing a heat-sealing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for lamination. The smoothing process can be performed using a commercially available laminator. Lamination and smoothing may be performed continuously using the commercially available vacuum laminator mentioned above.

[0211] The support may be removed between steps (I) and (II), or after step (II).

[0212] In step (II), the resin composition layer is cured (e.g., by thermal curing) to form an insulating layer made of the cured resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions commonly used when forming an insulating layer for a printed circuit board may be used.

[0213] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0214] Prior to thermal curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermal curing the resin composition layer, it may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0215] In manufacturing printed circuit boards, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer. These steps (III) through (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed circuit boards. If the support is removed after step (II), the removal of the support may be carried out between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (II) through (V) may be repeated to form a multilayer circuit board.

[0216] In other embodiments, the printed circuit board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as when a resin sheet is used.

[0217] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed circuit board.

[0218] Step (IV) is a process for roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The procedure and conditions for the roughening process are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a printed circuit board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution in this order.

[0219] The swelling solution used for the roughening treatment is not particularly limited, but examples include alkaline solutions and surfactant solutions, and is preferably an alkaline solution, with sodium hydroxide solution and potassium hydroxide solution being more preferred. Examples of commercially available swelling solutions include "Swelling Dip Securing P" and "Swelling Dip Securing SBU" manufactured by Atotec Japan. The swelling treatment with the swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0220] The oxidizing agent used for the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with 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 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Attec Japan.

[0221] Furthermore, an acidic aqueous solution is preferred as the neutralizing solution used in the roughening treatment. A commercially available example is "Reduction Solution Securigant P" manufactured by Attec Japan.

[0222] The neutralization treatment can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in a neutralization solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, it is preferable to immerse the object, which has been roughened with an oxidizing agent, in a neutralization solution at 40°C to 70°C for 5 to 20 minutes.

[0223] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. Also, the root mean square roughness (Rq) of the insulating layer surface after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0224] Step (V) is a step of forming a conductive layer, in which a conductive layer is formed on an insulating layer. The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductive layer may be a single-metal layer or an alloy layer, and examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). In particular, from the viewpoint of versatility in conductor layer formation, cost, and ease of patterning, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy are preferred, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy are more preferred, and single metal layers of copper are even more preferred.

[0225] The conductive layer may be a single-layer structure, or it may be a multi-layer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductive layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0226] The thickness of the conductor layer depends on the desired printed circuit board design, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0227] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using conventionally known techniques such as the semi-additive method or the fully additive method. From the viewpoint of ease of manufacture, it is preferable to form it by the semi-additive method. An example of forming the conductor layer by the semi-additive method is shown below.

[0228] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. Then, the unnecessary plating seed layer can be removed by etching or other means to form a conductor layer having the desired wiring pattern.

[0229] In other embodiments, the conductor layer may be formed using metal foil. When forming the conductor layer using metal foil, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed and the metal foil is laminated onto the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Subsequently, the metal foil on the insulating layer can be used to form a conductor layer having a desired wiring pattern by conventional known techniques such as the subtractive method or the modified semi-additive method.

[0230] Metal foils can be manufactured by known methods such as electrolysis and rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Oil & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0231] <Semiconductor device> The semiconductor device of the present invention includes the printed circuit board of the present invention. The semiconductor device of the present invention can be manufactured using the printed circuit board of the present invention.

[0232] Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Examples]

[0233] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. In the following, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "mass%", respectively. Unless otherwise specified, the temperature condition is room temperature (23°C), and unless the pressure condition is specified, the pressure condition is atmospheric pressure (1 atm).

[0234] <Synthesis Example 1: X-synthesis of maleimide> Maleimide A (m=1.47, Mw / Mn=1.81), represented by the following formula, was synthesized using the same method as in Synthesis Example 1 of the Japan Institute of Invention and Innovation, Technical Report No. 2020-500211, and a MEK solution of maleimide resin (62% by mass of non-volatile components) was obtained.

[0235] [ka]

[0236] <Adjustment Example 1: Adjustment of DMAP-tosylate> 2.0 g of 4-dimethylaminopyridine and 0.0164 moles of p-toluenesulfonic acid were weighed into a glass container, dimethyl sulfoxide was added so that the total solid content was 20% by weight, and the mixture was stirred for 30 minutes to dissolve and prepare a DMAP-tosylate solution.

[0237] <Adjustment Example 2: Adjustment of DMAP-phthalate> 2.0 g of 4-dimethylaminopyridine and 0.0164 moles of phthalic acid were weighed into a glass container, dimethyl sulfoxide was added so that the total solid content was 20% by weight, and the mixture was stirred for 30 minutes to dissolve and prepare a DMAP-phthalate solution.

[0238] <Adjustment Example 3: Adjustment of DMAP-trimellitate> 2.0 g of 4-dimethylaminopyridine and 0.0164 moles of trimellitic acid were weighed into a glass container, dimethyl sulfoxide was added so that the total solid content was 20% by weight, and the mixture was stirred for 30 minutes to dissolve and prepare a DMAP-trimellitic acid solution.

[0239] <Examples 1-6, Comparative Examples 1 and 2: Preparation of Resin Compositions> Each component was weighed according to the proportions of parts by mass listed in Table 1, and then 5 parts of MEK and 15 parts of cyclohexanone were added and uniformly dispersed using a high-speed rotary mixer to prepare a varnish-like resin composition. The details of each component listed in Table 1 are as follows.

[0240] (A) Maleimide resin MIR-3000-70MT: Maleimide resin with a biphenyl skeleton, maleimide group equivalent 393 g / eq., toluene solution with 70% non-volatile content, manufactured by Nippon Kayaku Co., Ltd. • Maleimide X: Maleimide resin with an indane skeleton, maleimide group equivalent 428 g / eq., synthesized in Synthesis Example 1. • SLK-6895-T90: Maleimide resin having a carbon skeleton derived from dimer acid, maleimide group equivalent 345 g / eq., toluene solution with 90% non-volatile content, manufactured by Shin-Etsu Chemical Co., Ltd.

[0241] (B) Salt of an amine compound represented by formula (I) • DMAP-tosylate: 20% by mass of non-volatile content, prepared according to Preparation Example 1 • DMAP-phthalate: 20% by mass of non-volatile content, prepared according to Preparation Example 2 • DMAP-trimellitic salt: 20% by mass of non-volatile content, prepared according to Preparation Example 3. • DMAP: 4-dimethylaminopyridine • 1B2PZ: 1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemicals Co., Ltd.

[0242] (C) Inorganic filler • SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.), with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m². 2 / g, manufactured by Admatex Corporation

[0243] (D) Anionic curing agent LA-3018-50P: Phenolic curing agent, 1-methoxy-2-propanol solution with a functional group equivalent of 151 g / eq. and a non-volatile content of 50% by mass, manufactured by DIC Corporation. • SA90: Phenolic curing agent, functional group equivalent 800g / eq., manufactured by SABIC. • HPC-8000-65T: Active ester-based curing agent, functional group equivalent 223 g / eq., toluene solution with 65% non-volatile content, manufactured by DIC Corporation. • V-03: Carbodiimide-based curing agent, functional group equivalent 216 g / eq., toluene solution with 50% non-volatile content by mass, manufactured by Nisshinbo Chemical Co., Ltd.

[0244] (E) Epoxy resin HP-4032-SS: Naphthalene-type epoxy resin, functional group equivalent 144 g / eq., manufactured by DIC Corporation. • NC3000L: Biphenyl-type epoxy resin, functional group equivalent 269 g / eq., manufactured by Nippon Kayaku Co., Ltd.

[0245] (F)Thermoplastic resin • YX7553BH30: Phenoxy resin, 1:1 solution of MEK and cyclohexanone with 30% non-volatile content by mass, manufactured by Mitsubishi Chemical Corporation. • PIAD200: Polyimide resin, a mixed solution of cyclohexanone with 30% non-volatile content, dimethyl glycol, and methylcyclohexane, manufactured by Arakawa Chemical Co., Ltd. • P2000: Styrene-based elastomer, manufactured by Asahi Kasei Corporation.

[0246] (G) Radical polymerization initiator • Perhexyl D: Peroxide-based radical polymerization initiator, di-tert-hexyl peroxide, manufactured by NOF Corporation.

[0247] <Test Example 1: Measurement of Glass Transition Temperature (Tg)> (1) Preparation of resin sheet A with a resin composition layer thickness of 40 μm A polyethylene terephthalate film (Lintec Corporation's "AL5", 38 μm thick) with a release layer was prepared as a support. The resin varnish obtained in the examples and comparative examples was uniformly applied to 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 (average 90°C) for 2 minutes to obtain a resin sheet A including the support and the resin composition layer.

[0248] (2) Preparation of hardened material The obtained resin sheet A was cured in an oven at 190°C for 90 minutes. By peeling the support from the resin sheet A after removing it from the oven, a cured resin composition layer was obtained.

[0249] (3) Measurement of glass transition temperature (Tg) The resulting cured material was cut into test specimens approximately 5 mm wide and 15 mm long, and thermomechanical analysis was performed using a thermomechanical analyzer (Rigaku Corporation's "Thermo Plus TMA8310") by the tensile loading method. After mounting the test specimens in the apparatus, the coefficient of thermal expansion (ppm) was measured twice consecutively under measurement conditions of a load of 1 g and a heating rate of 5°C / min. The average linear expansion coefficient (ppm / °C) was calculated from the coefficient of thermal expansion values ​​from 25°C to 150°C in the second measurement. The glass transition temperature (Tg;°C) was calculated in the second measurement.

[0250] <Test Example 2: Measurement of copper foil adhesion strength (copper foil peel strength)> The adhesion of the metal foil was evaluated by measuring the copper foil peel strength using the following procedure.

[0251] (1) Pre-treatment of copper foil The glossy surface of electrolytic copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd., 35 μm thick) was etched to a thickness of 1 μm with a micro-etching agent (CZ8101, manufactured by MEC Corporation) to roughen the copper surface, and then a rust-preventive treatment (CL8300) was applied. Copper foil whose surface has been etched with the above micro-etching agent is sometimes referred to as "CZ copper foil" below. Furthermore, this copper foil was heated in an oven at 130°C for 30 minutes to obtain copper foil I having a roughened surface.

[0252] (2) Preparation of inner layer substrate A glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") was prepared, with copper foil on the surface and an inner layer circuit formed on it. Both sides of this glass cloth substrate epoxy resin double-sided copper-clad laminate were etched to a thickness of 1 μm with a micro-etching agent (MEC "CZ8101") to roughen the surface of the copper foil. As a result, an inner layer substrate having a CZ copper foil with a treated surface was obtained.

[0253] (3) Lamination of resin composition layers The resin sheet A prepared in Test Example 1(1) was laminated to both sides of the inner layer substrate. This lamination was performed using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700") so that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by reducing the pressure to 13 hPa or less by depressurizing for 30 seconds, and then pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was heat-pressed at 100°C and a pressure of 0.5 MPa for 60 seconds. After that, the support was peeled off to expose the resin composition layer.

[0254] (4) Lamination of copper foil and curing of resin composition layer The treated surface of the copper foil I was laminated onto the exposed resin composition layer under the same conditions as described in "(3) Lamination of the resin composition layer". The resin composition layer was then cured at 200°C for 90 minutes to form an insulating layer containing the cured resin composition. Through the above operations, an evaluation substrate C was obtained in which CZ copper foil was laminated on both sides of the insulating layer. This evaluation substrate C had a layer structure of copper foil I / insulating layer / inner layer substrate / insulating layer / copper foil I.

[0255] (5) Measurement of copper foil adhesion strength (copper foil peel strength) The evaluation substrate C was cut into small pieces measuring 150 mm x 30 mm. A cut was made in the copper foil I of each piece using a cutter, enclosing a section 10 mm wide and 100 mm long. One end of this section was peeled off and grasped with the grips of a tensile tester (Autocom universal tester "AC-50C-SL" manufactured by TSE Corporation). At room temperature (25°C), the sample was pulled vertically at a speed of 50 mm / min, and the load [kgf / cm] when 35 mm was peeled off was measured as the copper foil adhesion strength. The sample after measurement was subjected to an accelerated environment test (HAST test) for 100 hours at 130°C and 85% RH using an advanced accelerated life tester (PM422) manufactured by Kusumoto Chemical Co., Ltd. After that, the copper foil adhesion strength after HAST was determined by measuring it in the same way as the initial copper foil adhesion strength measurement. The measurements were performed in accordance with the Japanese Industrial Standard JIS C6481.

[0256] The measurement results for the test examples are summarized in Table 1 below.

[0257] [Table 1]

[0258] The results shown in Table 1 above indicate that by using a resin composition containing (A) maleimide resin and (B) an amine compound salt represented by formula (I), it is possible to obtain a cured product that maintains excellent copper foil adhesion strength even after accelerated environmental testing (HAST) and has a high glass transition temperature.

Claims

1. (A) Maleimide resin, and (B) Formula (I): 【Chemistry 1】 [In the formula, R １ , R ２ , R ３ , R ４ and R ５ Each of these independently represents a hydrogen atom or a substituent. R ３ represents -OH, -SH, -NH ２ , -OR ｓ１ , -NHR ｓ１ , -N(R ｓ１ ) ２ , -OCOR ｓ１ , -NHCOR ｓ１ , or -SR ｓ１ represents R ｓ１ These are, independently, a halogen atom, a heteroaryl group, -CN, and -NO. ２ , -OH, -SH, -NH ２ -CHO, -OR ｓ２ , - NHR ｓ２ , -N(R ｓ２ ) ２ , -COR ｓ２ , -COOR ｓ２ , -OCOR ｓ２ , -CONHR ｓ２ ,-NHCOR ｓ２ , -SR ｓ２ , -SO ２ R ｓ２ This represents a monovalent hydrocarbon group which may be substituted with substituents such as, R ｓ２ Each of these independently represents a monovalent hydrocarbon group. An amine compound represented by formula (IIa): 【Chemistry 2】 [In the formula, X is -CO- or -SO ２ - indicates; R ａ , R ｂ , R ｃ , R ｄ and R ｅ Each of these independently represents either a hydrogen atom or a substituent. A resin composition containing a salt with an organic acid represented by [the specified formula].

2. R ３ However, -N(R ｓ１ ) ２ The resin composition according to claim 1.

3. The resin composition according to claim 1, wherein the amine compound represented by formula (I) is 4-dimethylaminopyridine.

4. (B) Component is an amine compound represented by formula (I) and the acid dissociation constant (pKa) in water at 25°C (in the case of polyhydric organic acids, the lowest acid dissociation constant (pK) in the first step). ａ１ The resin composition according to claim 1, comprising a salt with an organic acid whose pH is 3.0 or less.

5. The resin composition according to claim 1, wherein component (B) comprises a salt of an amine compound represented by formula (I) and an organic acid selected from phthalic acid, trimellitic acid, and p-toluenesulfonic acid.

6. The resin composition according to claim 1, wherein the mass ratio of component (B) to component (A) (content of component (B) / content of component (A)) is 0.001 to 0.

1.

7. (C) The resin composition according to claim 1, further comprising an inorganic filler.

8. The resin composition according to claim 7, wherein component (C) contains silica.

9. The resin composition according to claim 7, wherein the content of component (C) is 40% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass.

10. (D) The resin composition according to claim 1, wherein the content of the anionic polymerizable curing agent is 0% to 20% by mass, when the nonvolatile components in the resin composition are considered to be 100% by mass.

11. (E) The resin composition according to claim 1, wherein the epoxy resin content is 0% to 20% by mass, when the non-volatile components in the resin composition are considered to be 100% by mass.

12. (F) The resin composition according to claim 1, wherein the content of thermoplastic resin is 0% to 30% by mass, when the nonvolatile components in the resin composition are taken as 100% by mass.

13. The resin composition according to claim 1, wherein the glass transition temperature (Tg) of the cured product of the resin composition is 140°C or higher.

14. The resin composition according to claim 1, for forming an insulating layer on a printed circuit board.

15. A cured product of the resin composition according to any one of claims 1 to 14.

16. A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 14, provided on the support.

17. A printed circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 14.

18. A semiconductor device comprising a printed circuit board as described in claim 17.

19. Equation (I): 【Transformation 3】 [In the formula, R １ , R ２ , R ３ , R ４ and R ５ Each of these independently represents a hydrogen atom or a substituent. R ３ -OH, -SH, -NH ２ , -OR ｓ１ , - NHR ｓ１ , -N(R ｓ１ ) ２ , -OCOR ｓ１ ,-NHCOR ｓ１ , or -SR ｓ１ Show, R ｓ１ These are, independently, a halogen atom, a heteroaryl group, -CN, and -NO. ２ , -OH, -SH, -NH ２ -CHO, -OR ｓ２ , - NHR ｓ２ , -N(R ｓ２ ) ２ , -COR ｓ２ , -COOR ｓ２ , -OCOR ｓ２ , -CONHR ｓ２ ,-NHCOR ｓ２ , -SR ｓ２ , -SO ２ R ｓ２ This represents a monovalent hydrocarbon group which may be substituted with substituents such as, R ｓ２ Each of these independently represents a monovalent hydrocarbon group. An amine compound represented by formula (IIa): 【Chemistry 4】 [In the formula, X is -CO- or -SO ２ - indicates; R ａ , R ｂ , R ｃ , R ｄ and R ｅ Each of these independently represents either a hydrogen atom or a substituent. A maleimide resin curing accelerator containing a salt with an organic acid represented by [the specified formula].

Images