resin composition

Abstract

To provide a resin composition that yields a cured product with low dielectric loss tangent and excellent bending resistance.SOLUTION: A resin composition comprises (A) polyimide resin, (B) thermosetting resin, and (C) inorganic filler, wherein the component (A) includes polyimide resin containing one or more groups represented by formula (1) within a single molecule (where, the symbols in formula (1) are as defined in the attached specifications).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition, and further to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked. In build-up manufacturing methods, the insulating layers are generally formed by curing a resin composition containing an epoxy resin and an inorganic filler.

[0003] Printed wiring boards are required to have a low dielectric loss tangent to reduce transmission loss. On the other hand, materials with high strength, particularly bending resistance, are also required to improve the reliability of printed wiring boards. A method for improving bending resistance is known in which a polyimide resin is blended into the resin material (Patent Documents 1 and 2), but this is not sufficient. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-172663 [Patent Document 2] Patent No. 6805338 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin composition that can give a cured product having a low dielectric loss tangent and good bending resistance. [Means for solving the problem]

[0006] In order to achieve the objects of the present invention, the present inventors have conducted extensive research and have unexpectedly found that, in a resin composition comprising (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, by using a polyimide resin having a group represented by formula (1) described below as the polyimide resin (A), it is possible to obtain a cured product having a low dielectric tangent and good bending resistance compared to when conventional polyimide resins are used, and have thus completed the present invention.

[0007] That is, the present invention includes the following. [1] A resin composition comprising (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, The component (A) is a compound represented by the formula (1):

[0008] [ka]

[0009] [In the formula, (i)R 1 and R 2 each independently represents a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and R 1 and R 2 at least one of is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group, or (ii)R 1 and R 2 are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; * indicates the binding site.] A resin composition comprising a polyimide resin having one or more groups represented by the following formula (I): [2] The component (A) is a compound represented by the formula (2):

[0010] [ka]

[0011] [In the formula, X's each independently represent a divalent organic group consisting of five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; Y's each independently represent a tetravalent organic group consisting of five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; (i)R 1 and R 2 each independently represents a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and R 1 and R 2 at least one of is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group, or (ii)R 1 and R 2 are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; n represents the average number of repeating units, which is 1 or more. The resin composition according to [1] above, comprising a polyimide resin represented by the formula: [3] The resin composition according to [2] above, wherein X is a divalent organic group consisting of five or more skeletal atoms selected from carbon, oxygen, and sulfur atoms and non-skeletal atoms selected from hydrogen and halogen atoms, and when the n+1 Xs are taken as 100 mol %, 1 mol % to 80 mol % of them are divalent organic groups without an aromatic ring, and 20 mol % to 99 mol % are divalent organic groups with an aromatic ring. [4] The resin composition according to [2] above, wherein Y is a tetravalent organic group having five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms, and having an aromatic ring. [5] The resin composition according to the above [1], wherein the content of component (A) is 5% by mass or less, assuming that the total amount of non-volatile components in the resin composition is 100% by mass. [6] The resin composition according to the above [1], wherein the weight average molecular weight of component (A) is 10,000 or more. [7] The resin composition according to the above [1], wherein the component (B) contains an epoxy resin (B1). [8] The resin composition according to the above [7], wherein the component (B) contains an epoxy resin curing agent (B2). [9] The resin composition according to the above [8], wherein the component (B2) contains an active ester curing agent.

[10] The resin composition according to the above [8], wherein the component (B2) contains a phenol-based curing agent.

[11] The resin composition according to the above [1], wherein the component (B) includes a resin (B3) having a radical reactive group.

[12] The resin composition according to the above [1], wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 5 to 100.

[13] The resin composition according to the above [1], wherein the content of the component (C) is 50% by mass or more, assuming that the total amount of non-volatile components in the resin composition is 100% by mass.

[14] The resin composition according to the above [1], wherein the dielectric loss tangent (Df) of a cured product of the resin composition is 0.003 or less when measured at 5.8 GHz and 23°C.

[15] The resin composition according to the above [1], which is used to form an insulating layer of a semiconductor chip package.

[16] A cured product of the resin composition according to any one of [1] to

[14] above.

[17] A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of [1] to

[14] above.

[18] A printed wiring board having an insulating layer made of a cured product of the resin composition according to any one of [1] to

[14] above.

[19] A semiconductor device comprising the printed wiring board according to

[18] above. [Effects of the Invention]

[0012] According to the resin composition of the present invention, a cured product having a low dielectric loss tangent and good bending resistance can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0014] <Resin composition> The resin composition of the present invention is a resin composition containing (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, wherein the polyimide resin (A) contains a polyimide resin having one or more groups represented by the following formula (1) in each molecule. Such a resin composition can provide a cured product with a low dielectric loss tangent and good bending resistance.

[0015] The resin composition of the present invention may further contain optional components in addition to (A) the polyimide resin, (B) the thermosetting resin, and (C) the inorganic filler, such as (D) a curing accelerator, (E) a radical polymerization initiator, (F) other additives, and (G) an organic solvent.

[0016] Each component contained in the resin composition will be described in detail below.

[0017] <(A) Polyimide resin> The resin composition of the present invention contains (A) a polyimide resin. (A) Polyimide resin is a resin having an imide bond in the repeating unit. (A) Polyimide resin also includes modified polyimide resins such as siloxane-modified polyimide resins.

[0018] In the resin composition of the present invention, the polyimide resin (A) is a polyimide resin represented by the formula (1):

[0019] [ka]

[0020] [In the formula, (i)R 1 and R 2 each independently represents a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and R 1 and R 2 at least one of is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group, or (ii)R 1 and R 2 are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; * indicates the binding site.] The polyimide resin includes a polyimide resin having one or more groups represented by the following formula in one molecule:

[0021] A monovalent hydrocarbon group is a monovalent hydrocarbon group having one or more (preferably 1 to 50, more preferably 1 to 20) carbon atoms as skeletal atoms and hydrogen atoms as non-skeletal atoms. The monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group. The 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, alkylaralkyl groups, alkenylaryl groups, and alkenylaralkyl groups.

[0022] The monovalent ethylenically unsaturated bond-containing hydrocarbon group refers to a monovalent hydrocarbon group having one or more non-aromatic carbon-carbon double bonds. The monovalent ethylenically unsaturated bond-containing hydrocarbon group may or may not have an aromatic structure in addition to the ethylenically unsaturated bond. Examples of the monovalent ethylenically unsaturated bond-containing hydrocarbon group include an alkenyl group, an alkenylaryl group, and an alkenylaralkyl group, with an alkenyl group being preferred.

[0023] The alkyl group refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl group is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a tert-octyl group, a cyclopentyl group, a cyclohexyl group, and a cyclohexylmethyl group.

[0024] The 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, the alkenyl group is preferably an alkenyl group having 2 to 14 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, still more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably an alkenyl group having 2 or 3 carbon atoms. Examples of alkenyl groups include vinyl groups, propenyl groups (allyl groups, 1-propenyl groups, isopropenyl groups), butenyl groups (1-butenyl groups, crotyl groups, methallyl groups, isocrotyl groups, etc.), pentenyl groups (1-pentenyl groups, etc.), hexenyl groups (1-hexenyl groups, etc.), heptenyl groups (1-heptenyl groups, etc.), octenyl groups (1-octenyl groups, etc.), cyclopentenyl groups (2-cyclopentenyl groups, etc.), and cyclohexenyl groups (3-cyclohexenyl groups).

[0025] The aryl group refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, the aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0026] The aralkyl group refers to an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, the aralkyl group is preferably an aralkyl group having 7 to 15 carbon atoms, more preferably an aralkyl group having 7 to 11 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, a hydrocinnamyl group, an α-methylbenzyl group, an α-cumyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

[0027] The alkylaryl group refers to an aryl group substituted with one 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 a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 4-ethylphenyl group, a 3-ethylphenyl group, a 2-ethylphenyl group, a 4-isopropylphenyl group, a 3-isopropylphenyl group, and a 2-isopropylphenyl group.

[0028] The alkylaralkyl group refers to an aralkyl group in which an aromatic carbon atom is substituted with one or more (preferably one) alkyl group. Unless otherwise specified, the alkylaralkyl group is preferably an alkylaralkyl group having 8 to 16 carbon atoms, more preferably an alkylaralkyl group having 8 to 12 carbon atoms. Examples of the alkylaralkyl group include a 4-methylbenzyl group, a 3-methylbenzyl group, a 2-methylbenzyl group, a 4-ethylbenzyl group, a 3-ethylbenzyl group, a 2-ethylbenzyl group, a 4-isopropylbenzyl group, a 3-isopropylbenzyl group, and a 2-isopropylbenzyl group.

[0029] The alkenylaryl group refers to an aryl group substituted with one or more (preferably one) alkenyl groups. Unless otherwise specified, the alkenylaryl group is preferably an alkenylaryl group having 8 to 15 carbon atoms, more preferably an alkenylaryl group having 8 to 11 carbon atoms. Examples of the alkenylaryl group include a 4-vinylphenyl group, a 3-vinylphenyl group, a 2-vinylphenyl group, a 4-isopropenylphenyl group, a 3-isopropenylphenyl group, and a 2-isopropenylphenyl group.

[0030] The alkenylaralkyl group refers to an aralkyl group in which an aromatic carbon atom is substituted with one or more (preferably one) alkenyl groups. Unless otherwise specified, the alkenylaralkyl group is preferably an alkenylaralkyl group having 9 to 16 carbon atoms, more preferably an alkylaralkyl group having 9 to 12 carbon atoms. Examples of the alkenylaralkyl group include a 4-vinylbenzyl group, a 3-vinylbenzyl group, a 2-vinylbenzyl group, a 4-isopropenylbenzyl group, a 3-isopropenylbenzyl group, and a 2-isopropenylbenzyl group.

[0031] A divalent hydrocarbon group is a divalent unsaturated hydrocarbon group having one or more (preferably 1 to 50, more preferably 1 to 20) carbon atoms as skeletal atoms and hydrogen atoms as non-skeletal atoms, with one atom forming a non-aromatic double bond to which it is bonded. The divalent hydrocarbon group may or may not have an aromatic structure apart from the double bond formed with the atom to which it is bonded. Examples of divalent hydrocarbon groups include alkylidene groups.

[0032] An alkylidene group refers to a straight-chain, branched-chain, and / or cyclic divalent aliphatic hydrocarbon group consisting of only single bonds, excluding a double bond formed with one bonding atom. Unless otherwise specified, the alkylidene group is preferably an alkylidene group having 1 to 14 carbon atoms, more preferably an alkylidene group having 1 to 10 carbon atoms, even more preferably an alkylidene group having 1 to 6 carbon atoms, and particularly preferably an alkylidene group having 1 to 3 carbon atoms. Examples of the alkylidene group include a methylidene group (=CH2), an ethylidene group (=CHCH3), a propylidene group (=CHCH2CH3), an isopropylidene group (=C(CH3)2), and a butylidene group (=CHCH2CH2CH3).

[0033] The term "ethylenically unsaturated bond-containing carbocycle" refers to a non-aromatic ring whose only ring-constituting atoms are carbon atoms having a non-aromatic carbon-carbon double bond. The ethylenically unsaturated bond-containing carbocycle is preferably a 5- to 18-membered ethylenically unsaturated bond-containing carbocycle, and more preferably a 5- to 14-membered ethylenically unsaturated bond-containing carbocycle. Examples of the ethylenically unsaturated bond-containing carbocycle include monocyclic ethylenically unsaturated bond-containing carbocycles such as a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring; bicyclic ethylenically unsaturated bond-containing carbocycles such as a bicyclo[2.2.1]hept-2-ene ring (norbornene ring), a bicyclo[2.2.2]oct-2-ene ring, and a bicyclo[4.4.0]dec-2-ene ring; and tricyclo[5.2.1.0]hept-2-ene ring. 2,6 ] Tricyclic ethylenically unsaturated bond-containing carbocyclic rings such as a dec-3-ene ring are also included.

[0034] The term "ethylenically unsaturated bond-containing heterocycle" refers to a non-aromatic ring having a non-aromatic carbon-carbon double bond and containing heteroatoms such as oxygen, nitrogen, and sulfur atoms in addition to carbon atoms as ring-constituting atoms. The ethylenically unsaturated bond-containing heterocycle is preferably a 5- to 18-membered ethylenically unsaturated bond-containing heterocycle, and more preferably a 5- to 14-membered ethylenically unsaturated bond-containing heterocycle. Examples of the ethylenically unsaturated bond-containing heterocycle include bicyclic ethylenically unsaturated bond-containing carbocyclic rings such as a 7-oxabicyclo[2.2.1]hepta-2-ene ring.

[0035] In the first embodiment, R 1 and R 2 each independently represents a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and R 1 and R 2 at least one of is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group; preferably, it is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, an alkylaralkyl group, an alkenylaryl group, or an alkenylaralkyl group, and R 1 and R 2 At least one of R is an alkenyl group, an alkenylaryl group, an alkenylaralkyl group, or an alkylidene group; more preferably, it is a hydrogen atom, an alkenyl group, or an alkylidene group, and R 1 and R 2 At least one of R is an alkenyl group or an alkylidene group; particularly preferably, R 1 is an alkenyl group or an alkylidene group, and R 2 is a hydrogen atom.

[0036] In the second embodiment, R 1 and R 2are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; preferably a 5- to 18-membered ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a group selected from alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkylaryl groups, alkylaralkyl groups, alkenylaryl groups, and alkenylaralkyl groups, or a 5- to 18-membered ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a group selected from alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkylaryl groups, alkylaralkyl groups, alkenylaryl groups, and alkenylaralkyl groups. It forms a 5- to 18-membered ethylenically unsaturated bond-containing heterocyclic ring which may be substituted with a group selected from the group consisting of methyl, ...

[0037] In one embodiment, the polyimide resin (A) is preferably represented by the formulas (1a) to (1h):

[0038] [ka]

[0039] [In the formula, R a1 , R a2 , R a3 , R a4 , R b1 , R b2 , R b3 , R b4 , R b5 , R b6 , R c1 , R c2 , R c3 , R c4 , Rc5 , R c6 , R d1 , R d2 , R d3 , R d4 , R e1 , R e2 , R e3 , R e4 , R e5 , R e6 , R e7 , R f1 , R f2 , R f3 , R f4 , R f5 , R g1 , R g2 , R g3 , R h1 and R h2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; X a represents -O-, -CH2-, or -CH2CH2-; * indicates the binding site.] More preferably, the polyimide resin has one or more groups selected from the formulae (1a), (1b), (1f) and (1h) in one molecule; and particularly preferably, the polyimide resin has one or more groups selected from the formulae (1-1) to (1-12):

[0040] [ka]

[0041] [wherein * indicates a binding site.] The polyimide resin includes a polyimide resin having one or more groups selected from the following in one molecule.

[0042] In one embodiment, the (A) polyimide resin preferably has the formula (2):

[0043] [ka]

[0044] [In the formula, X's each independently represent a divalent organic group consisting of five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; Y's each independently represent a tetravalent organic group consisting of five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; n indicates the average number of repeating units, which is 1 or more; Other symbols are the same as in formula (1). The polyimide resin includes a polyimide resin represented by the formula:

[0045] Each X independently represents a divalent organic group consisting of 5 or more (preferably 5 to 200, more preferably 5 to 100, and even more preferably 5 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms.

[0046] X may be a divalent organic group having no aromatic ring, or may be a divalent organic group having an aromatic ring. However, from the viewpoint of further improving flexibility, it is preferable that one or more of the n+1 Xs be a divalent organic group having no aromatic ring, and one or more be a divalent organic group having no aromatic ring; when the n+1 Xs are 100 mol%, it is preferable that 1 mol% to 99 mol% of them be a divalent organic group having no aromatic ring, and 1 mol% to 99 mol% be a divalent organic group having an aromatic ring; from the viewpoint of further optimizing the glass transition temperature, It is more preferable that 1 mol% to 90 mol% of them are divalent organic groups having no aromatic ring, and 10 mol% to 99 mol% are divalent organic groups having an aromatic ring; it is even more preferable that 1 mol% to 80 mol% of them are divalent organic groups having no aromatic ring, and 20 mol% to 99 mol% are divalent organic groups having an aromatic ring; it is particularly preferable that 20 mol% to 80 mol% of them are divalent organic groups having no aromatic ring, and 20 mol% to 80 mol% are divalent organic groups having an aromatic ring.

[0047] In one embodiment, the divalent organic group having an aromatic ring for X is preferably represented by any one of the formulae (X1) to (X5):

[0048] [ka]

[0049] [In the formula, R A each independently represents a substituent; each a independently represents 0, 1, 2, or 3; X 2a , X 3a , X 3b , X 4a , X 4b , X 4c , X 5a , X 5b , X 5c and X 5d are each independently a single bond, -C(R s )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R s each independently represents a hydrogen atom or an alkyl group; Ring X 31 , Ring X 41 , Ring X 42 , Ring X 51 , Ring X 52 and ring X 53 each independently represents an aromatic ring which may have a substituent or a non-aromatic ring which may have a substituent; * indicates the binding site.] is a group selected from

[0050] R A each independently represents a substituent, and in one embodiment, is preferably an alkyl group.

[0051] R AThe "substituent" in the formula (I) is not particularly limited, and examples thereof include monovalent substituents such as halogen atoms, -NO, -CN, -COH, -OH, -SH, -NH, -COOH, -R, -COR, -OR, -SR, -SOR, -SOR, -SOR, -NHR, -N(R), -COOR, -OCOR, -CONH, -CONHR, -CON(R), and -NHCOR (wherein each R independently represents a monovalent hydrocarbon group).

[0052] Each a independently represents 0, 1, 2, or 3; in one embodiment, it is preferably 0, 1, or 2; more preferably 0 or 1; and even more preferably 0.

[0053] X 2a , X 3a , X 3b , X 4a , X 4b , X 4c , X 5a , X 5b , X 5c and X 5d are each independently a single bond, -C(R s )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, and in one embodiment, preferably represents a single bond, -C(R s )2- or -O-. s each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0054] Ring X 31 , Ring X 41 , Ring X 42 , Ring X 51 , Ring X 52 and ring X 53 each independently represents an aromatic ring which may have a substituent, or a non-aromatic ring which may have a substituent; in one embodiment, it is preferably an aromatic ring which may have a substituent, more preferably a benzene ring which may have a substituent, and even more preferably a benzene ring which may be substituted with an alkyl group.

[0055] Ring X 31 , Ring X 41 , Ring X 42 , Ring X 51 , Ring X 52 and ring X 53 The "substituents" in the "optionally substituted aromatic ring" and "optionally substituted non-aromatic ring" are R A Examples of the substituents are the same as those in the above.

[0056] The aromatic ring refers to a ring that conforms to Hückel's rule, in which the number of electrons contained in the π-electron system on the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocycle containing only carbon atoms as ring-constituting atoms, or an aromatic heterocycle containing heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring-constituting atoms in addition to carbon atoms. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring. Suitable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, with a benzene ring or a naphthalene ring being more preferred, and a benzene ring being particularly preferred. The aromatic ring may be an aromatic ring partially condensed with a non-aromatic ring. Examples of the aromatic ring partially condensed with a non-aromatic ring include an indane ring, an indene ring, a tetralin ring, a 1,2-dihydronaphthalene ring, a 1,4-dihydronaphthalene ring, a fluorene ring, a 9,10-dihydroanthracene ring, and a 9,10-dihydrophenanthrene ring.

[0057] The non-aromatic ring refers to a ring other than an aromatic ring that has aromaticity throughout the ring. The non-aromatic ring may be a non-aromatic carbocyclic ring having only carbon atoms as ring-constituting atoms, or a non-aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring-constituting atoms in addition to carbon atoms. The non-aromatic ring may be a saturated ring or an unsaturated ring. The non-aromatic ring is preferably a 3- to 21-membered non-aromatic ring, more preferably a 4- to 17-membered non-aromatic ring, and even more preferably a 5- to 14-membered non-aromatic ring. Specific preferred examples of the non-aromatic ring include monocyclic non-aromatic saturated carbocyclic rings such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; monocyclic non-aromatic unsaturated carbocyclic rings such as a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, and a cyclohexadiene ring; bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decalin ring), bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring (hydrindane ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[3.3.0]octane ring, bicyclo[3.3.1]nonane ring, 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 bicyclo[2.2.1]hept-2-ene ring (norbornene ring), bicyclo[2.2.2]oct-2-ene ring, bicyclo[4.4.0]dec-2-ene ring, and the like.

[0058] Specific examples of the divalent organic group having an aromatic ring in X include, but are not limited to, those represented by the formulae (X-1) to (X-6):

[0059] [ka]

[0060] [wherein * indicates a binding site.] Examples of the group include a group selected from the following:

[0061] In one embodiment, the divalent organic group for X having no aromatic ring is preferably a divalent organic group having no aromatic ring but a non-aromatic ring, and more preferably a divalent organic group represented by formula (X6):

[0062] [ka]

[0063] [In the formula, Ring X 6 each independently represents a non-aromatic ring which may have a substituent; a1 and a2 each independently represent an integer of 0 or 1 or more; * indicates the binding site.] It is a group represented by the following formula:

[0064] Ring X 6 each independently represent a non-aromatic ring which may have a substituent; in one embodiment, preferably a monocyclic non-aromatic saturated carbocyclic ring which may have a substituent, or a monocyclic non-aromatic unsaturated carbocyclic ring which may have a substituent; more preferably a cyclohexane ring which may be substituted with a group selected from an alkyl group and an alkenyl group, or a cyclohexene ring which may be substituted with a group selected from an alkyl group and an alkenyl group; even more preferably a cyclohexane ring which may be substituted with a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms, or a cyclohexene ring which may be substituted with a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms.

[0065] a1 and a2 each independently represent an integer of 0 or 1 or more; in one embodiment, preferably, each independently represent an integer of 0 to 20; more preferably, each independently represent an integer of 1 to 20; and even more preferably, each independently represent an integer of 5 to 10.

[0066] Specific examples of the divalent organic group not having an aromatic ring in X include, but are not particularly limited to, those represented by the formulae (X-7) to (X-8):

[0067] [ka]

[0068] [wherein * indicates a binding site.] Examples of the group include a group selected from the following:

[0069] Each Y independently represents a tetravalent organic group consisting of 5 or more (preferably 5 to 200, more preferably 5 to 100, and even more preferably 5 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms.

[0070] Y may be a tetravalent organic group having no aromatic ring, or a tetravalent organic group having an aromatic ring, but is preferably a tetravalent organic group having an aromatic ring.

[0071] In one embodiment, the tetravalent organic group having an aromatic ring for Y is preferably represented by any one of the formulae (Y1) to (Y5):

[0072] [ka]

[0073] [In the formula, R B each independently represents a substituent; b's each independently represent 0, 1, or 2; Y 2a , Y 3a , Y 3b , Y 4a , Y 4b , Y 4c , Y 5a , Y 5b , Y 5c and Y 5dare each independently a single bond, -C(R t )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R t each independently represents a hydrogen atom or an alkyl group; Ring Y 31 , ring Y 41 , ring Y 42 , ring Y 51 , ring Y 52 and ring Y 53 each independently represents an aromatic ring which may have a substituent or a non-aromatic ring which may have a substituent; * indicates the binding site.] is a group selected from

[0074] R B each independently represents a substituent, and in one embodiment, is preferably an alkyl group.

[0075] R B The "substituents" in A Examples of the substituents are the same as those in the above.

[0076] Each b independently represents 0, 1, or 2; in one embodiment, it is preferably 0 or 1; and more preferably 0.

[0077] Y 2a , Y 3a , Y 3b , Y 4a , Y 4b , Y 4c , Y 5a , Y 5b , Y 5c and Y 5d are each independently a single bond, -C(R t )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, and in one embodiment, preferably represents a single bond, -C(R t )2- or -O-. teach independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0078] Ring Y 31 , ring Y 41 , ring Y 42 , ring Y 51 , ring Y 52 and ring Y 53 each independently represents an aromatic ring which may have a substituent, or a non-aromatic ring which may have a substituent; in one embodiment, it is preferably an aromatic ring which may have a substituent, more preferably a benzene ring which may have a substituent, and even more preferably a benzene ring which may be substituted with an alkyl group.

[0079] Ring Y 31 , ring Y 41 , ring Y 42 , ring Y 51 , ring Y 52 and ring Y 53 The "substituents" in the "optionally substituted aromatic ring" and "optionally substituted non-aromatic ring" are R A Examples of the substituents are the same as those in the above.

[0080] Specific examples of the divalent organic group having an aromatic ring in Y include, but are not limited to, those represented by the formulae (Y-1) to (Y-6):

[0081] [ka]

[0082] [wherein * indicates a binding site.] Examples of the group include a group selected from the following:

[0083] n represents the average number of repeating units of 1 or more; it is preferably 1 to 500, more preferably 1 to 100.

[0084] In one embodiment, the polyimide resin (A) is more preferably a polyimide resin represented by any one of the formulas (2a) to (2h):

[0085] [ka]

[0086] [In the formula, each symbol is the same as in formulas (1a) to (1h) and formula (2)] The polyimide resin preferably includes a polyimide resin represented by any one of the following formulas (2-1) to (2-12):

[0087] [ka]

[0088] [In the formula, each symbol is the same as in formula (2)] The polyimide resin includes any of the following:

[0089] The number-average molecular weight (Mn) of the (A) polyimide resin is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 4,000 or more, and particularly preferably 6,000 or more, with an upper limit of preferably 50,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and particularly preferably 12,000 or less. The weight-average molecular weight (Mw) of the (A) polyimide resin is preferably 2,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and particularly preferably 15,000 or more, with an upper limit of preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, and particularly preferably 25,000 or less. The polydispersity (Mw / Mn) of the polyimide resin (A) is preferably 1.1 to 10.0, more preferably 1.5 to 5.0, even more preferably 1.8 to 4.0, and particularly preferably 2.0 to 3.0. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) can be measured as polystyrene-equivalent values ​​by gel permeation chromatography (GPC).

[0090] The (A) polyimide resin can be produced by reacting a tetracarboxylic dianhydride, a diamine, and a dicarboxylic anhydride using a known method or a method similar thereto.

[0091] The content of the (A) polyimide resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, and the lower limit is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 0.8% by mass or more.

[0092] The content of the polyimide resin having one or more groups represented by formula (1) per molecule in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, and the lower limit is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 0.8% by mass or more.

[0093] <(B) Thermosetting resin> The resin composition of the present invention contains a (B) thermosetting resin. The (B) thermosetting resin described here is a component other than the (A) polyimide resin described above. Examples of the (B) thermosetting resin include epoxy resins, resins having radical reactive groups, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and silicone resins, and may also contain a curing agent (e.g., an epoxy resin curing agent) that can react with these resins to cure them.

[0094] <(B1) Epoxy resin> In one embodiment, the resin composition of the present invention preferably contains an epoxy resin (B1) as the thermosetting resin (B). The epoxy resin (B1) is a curable resin having an epoxy group and an epoxy equivalent of 5,000 g / eq. or less.

[0095] (B1) Examples of epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ether Examples of the epoxy resins include ester-type epoxy resins, cresol novolac-type epoxy resins, phenol aralkyl-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, and phenolphthalimidine-type epoxy resins. The (B1) epoxy resins may be used alone or in combination of two or more.

[0096] The resin composition of the present invention preferably contains, as the epoxy resin (B1), an epoxy resin having two or more epoxy groups per molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the epoxy resin (B1) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0097] (B1) Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only a liquid epoxy resin as the epoxy resin, or only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin, but it is particularly preferable that the resin composition contain both a liquid epoxy resin and a solid epoxy resin.

[0098] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0099] Preferred liquid epoxy resins include glycerol-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, glycidyl amine-type epoxy resins, phenol novolac-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, alicyclic glycidyl ethers, and epoxy resins having a butadiene structure.

[0100] Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "828EL", "825", and "Epikote 828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "jER807" and "1750" ( Bisphenol F epoxy resin; Mitsubishi Chemical Corporation's "jER152" (phenol novolac epoxy resin); Mitsubishi Chemical Corporation's "630", "630LSD", and "604" (glycidylamine epoxy resin); ADEKA Corporation's "ED-523T" (glycirol epoxy resin); ADEKA Corporation's "EP-3950L" and "EP-3980S" (glycidylamine epoxy resin); ADEKA Corporation's "EP-4088S" (dicyclopentadiene epoxy resin); Nippon Steel Chemical & Material Corporation's "ZX1059" (mixture of bisphenol A and bisphenol F epoxy resins); Nagase ChemteX Corporation's "EX-721" (glycidyl ester epoxy resin); Nagase ChemteX Corporation's "EX-991L" (epoxy resin containing alkyleneoxy and butadiene skeletons); Daicel Corporation's "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) ); "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resins having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EG-280" (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemicals Co., Ltd.; and "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Nagase ChemteX Corporation.

[0101] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0102] Preferred solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol novolac-type epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, and phenolphthalimidine-type epoxy resins.

[0103] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation; and "EXA-7311" and "E" manufactured by DIC Corporation. 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", and "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" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.These may be used alone or in combination of two or more.

[0104] When a liquid epoxy resin and a solid epoxy resin are used in combination as the (B1) epoxy resin, the mass ratio thereof (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.

[0105] The epoxy equivalent of the (B1) 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 the resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0106] The weight average molecular weight (Mw) of the epoxy resin (B1) 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 by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0107] The content of the (B1) epoxy resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 12% by mass or less; the lower limit is not particularly limited, but is, for example, 0% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0108] <(B2) Epoxy resin hardener> When the resin composition of the present invention contains an epoxy resin (B1) as the thermosetting resin (B), it may further contain an epoxy resin curing agent (B2) as an optional component. The epoxy resin curing agent (B2) may be used alone or in any combination of two or more. When the epoxy resin (B1) is contained as the thermosetting resin (B), the epoxy resin curing agent (B2) may have the function of reacting with the epoxy resin (B1) to cure it.

[0109] The (B2) epoxy resin curing agent is not particularly limited, but examples thereof include active ester curing agents, phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. In one embodiment, the (B2) epoxy resin curing agent preferably contains one or more epoxy resin curing agents selected from active ester curing agents, phenolic curing agents, and carbodiimide curing agents, and more preferably contains one or more epoxy resin curing agents selected from active ester curing agents and phenolic curing agents. In one embodiment, the (B2) epoxy resin curing agent particularly preferably contains an active ester curing agent from the viewpoint of further reducing the dielectric loss tangent. In one embodiment, the (B2) epoxy resin curing agent particularly preferably contains a phenolic curing agent from the viewpoint of further improving curability.

[0110] As the active ester curing agent, compounds having two or more highly reactive ester groups per 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 one 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. From the viewpoint of improving heat resistance in particular, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, 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 novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0111] Specific examples of the active ester curing agent include dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and active ester compounds containing a benzoylated product of phenol novolac, and among these, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

[0112] Commercially available active ester curing agents include "EXB9451," "EXB9460," "EXB9460S," "HPC-8000L-65TM," "HPC-8000-65T," "HPC-8000H," and "HPC-8000H-65TM" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; and "HP-B-8151-62T," "EXB-8100L-65T," "EXB-9416-70BK," and "HPC-8150-62T" as active ester compounds containing a naphthalene structure. and "EXB-8" (manufactured by DIC Corporation); a phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC Corporation); an active ester compound which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester compounds which are benzoylated products of phenol novolac, "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); an active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), and the like.

[0113] As the phenolic curing agent, a phenolic curing agent having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesion to an adherend, a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred. Among them, a triazine skeleton-containing phenolic novolac resin is preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenolic curing agents include "MEH-7700," "MEH-7810," and "MEH-7851" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-375," and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "LA-7052," "LA-7054," "LA-3018," "LA-3018-50P," "LA-1356," "TD2090," and "KA-1160" manufactured by DIC Corporation.

[0114] Examples of carbodiimide curing agents include curing agents having one or more, preferably two or more, carbodiimide structures in one molecule, such as aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane-bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); and aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). ; aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0115] Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P," "Stavaxol P400," and "Hykasil 510" manufactured by Rhein Chemie.

[0116] The acid anhydride curing agent may be a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferred. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples of suitable anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric anhydrides such as styrene-maleic acid resins, which are copolymers of styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100," "MH-700," "MTA-15," "DDSA," and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.; and "EF-30," "EF-40," "EF-60," and "EF-80" manufactured by Clay Valley.

[0117] Examples of the amine curing agent include curing agents having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, among which aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents may be used, and examples thereof include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0118] Specific examples of benzoxazine curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemicals Corporation.

[0119] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type multifunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer).

[0120] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0121] The reactive group equivalent of the epoxy resin curing agent (B2) is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the epoxy resin curing agent (B2) per equivalent of reactive group.

[0122] (B2) When a phenolic curing agent is included as the epoxy resin curing agent, the content of the phenolic curing agent in the resin composition, assuming that the non-volatile components in the resin composition are 100% by mass, is preferably 0.5% by mass or more from the viewpoint of further improving curability, and is preferably 5% by mass or less, more preferably 3% by mass or more, from the viewpoint of further reducing the dielectric loss tangent.

[0123] When an active ester curing agent is included as the epoxy resin (B2) curing agent, the content of the active ester curing agent in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more, from the viewpoint of further reducing the dielectric loss tangent, when the nonvolatile components in the resin composition are taken as 100% by mass. Furthermore, the content of the active ester curing agent in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, from the viewpoint of further reducing the dielectric loss tangent, when the epoxy resin (B2) curing agent in the resin composition is taken as 100% by mass.

[0124] The content of the (B2) epoxy resin curing agent in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 17% by mass or less. The lower limit is not particularly limited, but can be, for example, 0% by mass or more or 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0125] The mass ratio of the epoxy resin (B2) curing agent to the epoxy resin (B1) in the resin composition (component (B2) / component (B1)) is not particularly limited, but is preferably 0.5 or more, more preferably 1.0 or more, and particularly preferably 1.1 or more. The upper limit is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.

[0126] <(B3) Resin Having a Radical Reactive Group> The resin composition of the present invention preferably contains (B3) a resin having a radical reactive group as (B) the thermosetting resin. (B3) The resin having a radical reactive group has one or more (preferably two or more) radical reactive groups in one molecule. (B3) The resin having a radical reactive group may be used alone or in combination of two or more.

[0127] The radical-reactive group is a group having a radical-reactive ethylenically unsaturated bond, and examples thereof include, but are not limited to, (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, and (5) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group (for example, a vinylphenyl group (i.e., a 4-vinylphenyl group, a 3-vinylphenyl group, or a 2-vinylphenyl group), an isopropenylphenyl group (i.e., a 4-isopropenylphenyl group, a 3-isopropenylphenyl group, or a 2-isopropenylphenyl group). (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group (for example, a vinylbenzyl group (i.e., a 4-vinylbenzyl group, a 3-vinylbenzyl group, a 2-vinylbenzyl group), an isopropenylbenzyl group (i.e., a 4-isopropenylbenzyl group, a 3-isopropenylbenzyl group, a 2-isopropenylbenzyl group)), (7) a maleimide group (a 2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), and the like.

[0128] In the first embodiment, the resin having (B3) a radical reactive group preferably includes a resin having two or more radical reactive groups (for example, a number average molecular weight of 800 or more). The resin is not particularly limited, but examples thereof include phenoxy resin, polyvinyl acetal resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, and polyester resin. In this embodiment, the resin having (B3) a radical reactive group includes a modified resin having two or more radical reactive groups of these resins.

[0129] In the first embodiment, the resin (B3) having a radical reactive group more preferably includes a resin selected from a modified polyphenylene ether resin having two or more radical reactive groups and a modified polystyrene resin having two or more radical reactive groups, and even more preferably includes a modified polyphenylene ether resin having two or more radical reactive groups, and particularly preferably, in one embodiment, a resin represented by formula (3):

[0130] [ka]

[0131] [In the formula, R 11 and R 12 each independently represents an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each independently represents a hydrogen atom or an alkyl group; R a and R beach independently represent (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group; X 1 is a single bond, -C(R c )2-, -O-, -CO-, -S-, -SO-, or -SO2-; R c each independently represents a hydrogen atom or an alkyl group; s represents 0 or 1; t and u each independently represent an integer of 1 or more. The t units and u units may be the same or different for each unit.

[0132] R 11 and R 12 R each independently represents an alkyl group, and in one embodiment, is preferably a methyl group. 13 and R 14 R each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom. 21 and R 22 R each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. 23 and R 24 each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0133] R a and R beach independently represents (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group.

[0134] R a and R b are each independently preferably (1) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and optionally further substituted with an alkyl group, or (2) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and optionally further substituted with an alkyl group; more preferably a 4-vinylphenyl group, a 3-vinylphenyl group, a 2-vinylphenyl group, a 4-isopropenylphenyl group, a 3-isopropenylphenyl group, a 2-isopropenylphenyl group, a 4-vinylbenzyl group, a 3-vinylbenzyl group, a 2-vinylbenzyl group, a 4-isopropenylbenzyl group, a 3-isopropenylbenzyl group, or a 2-isopropenylbenzyl group; particularly preferably a 4-vinylbenzyl group, a 3-vinylbenzyl group, or a 2-vinylbenzyl group.

[0135] X 1 is a single bond, -C(R c )2-, -O-, -CO-, -S-, -SO-, or -SO2-, and in one embodiment, preferably represents a single bond, -C(R c )2- or -O-. c each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.

[0136] s represents 0 or 1, and in one embodiment, is preferably 1. t and u each independently represent an integer of 1 or more, and in one embodiment, is preferably an integer of 1 to 200, and more preferably an integer of 1 to 100.

[0137] The radical reactive group equivalent of the resin (B3) having a radical reactive group in the first embodiment is preferably 300 g / eq. to 2500 g / eq., more preferably 400 g / eq. to 2000 g / eq. The radical reactive group equivalent represents the mass of the resin (compound) per equivalent of the radical reactive group.

[0138] The number average molecular weight of the resin (B3) having a radical reactive group in the first embodiment is preferably 800 to 10000, more preferably 900 to 5000. The number average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0139] Examples of commercially available resins having a radical reactive group (B3) in the first embodiment include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company, Inc.; and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether resins) manufactured by SABIC Innovative Plastics.

[0140] In the second embodiment, the resin (B3) having a radical reactive group includes a low-molecular-weight compound (e.g., a molecular weight of less than 800) having two or more radical reactive groups. Examples of such compounds include polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800, polyfunctional vinylphenyl group-containing compounds having a molecular weight of less than 800, and polyfunctional (meth)allyl group-containing compounds having a molecular weight of less than 800.

[0141] A polyfunctional (meth)acryloyl group-containing compound having a molecular weight of less than 800 is a compound having two or more acryloyl groups or methacryloyl groups. Examples of polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800 include aliphatic (meth)acrylic acid ester compounds such as cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; dioxane Examples of the ether-containing (meth)acrylic acid ester compounds include ricol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate; and isocyanurate-containing (meth)acrylic acid ester compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate.Examples of commercially available polyfunctional (meth)acryloyl group-containing compounds having a molecular weight of less than 800 include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., and "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd.

[0142] A polyfunctional vinylphenyl group-containing compound having a molecular weight of less than 800 is a compound having two or more vinylphenyl groups. Examples of polyfunctional vinylphenyl group-containing compounds having a molecular weight of less than 800 include 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether.

[0143] A polyfunctional (meth)allyl group-containing compound having a molecular weight of less than 800 is a compound having two or more allyl or methallyl groups. Examples of polyfunctional (meth)allyl group-containing compounds having a molecular weight of less than 800 include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyldiphenylsilane. Commercially available polyfunctional (meth)allyl group-containing compounds with a molecular weight of less than 800 include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., "DAND" (2,3-diallyl naphthalenecarboxylate) manufactured by Nippon Distillation Industry Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Industry Co., Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemical Industry Co., Ltd.

[0144] In one embodiment of the second embodiment, the resin (B3) having a radical reactive group is particularly preferably a resin represented by formula (4):

[0145] [ka]

[0146] [In the formula, R d and R e each independently represent (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group; X 2 and X 3 represents a single bond or an alkylene group; Ring A is an optionally substituted non-aromatic carbocyclic ring or an optionally substituted non-aromatic heterocyclic ring. The compound includes a low molecular weight compound (for example, a molecular weight of less than 800) represented by the formula:

[0147] The "substituents" included in the definition of the symbols in formula (4) include R A Examples of the substituents are the same as those in the above.

[0148] R d and R e R each independently represents (1) an acryloyl group, (2) a methacryloyl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from a vinyl group and an isopropenyl group and which may further be substituted with an alkyl group. d and R e In one embodiment, each of is independently preferably an acryloyl group or a methacryloyl group.

[0149] X 2 and X 3represents a single bond or an alkylene group. The alkylene group refers to a straight-chain and / or branched-chain divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include -CH2-, -CH2-CH2-, -CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, -C(CH3)2-, -CH2-CH2-CH2-CH2-, -CH2-CH2-CH(CH3)-, -CH2-CH(CH3)-CH2-, -CH(CH3)-CH2-CH2-, -C(CH3)2-CH2-, and -CH2-C(CH3)2-. X 2 and X 3 In one embodiment, each independently is preferably an alkylene group.

[0150] Ring A is an optionally substituted non-aromatic carbocyclic ring or an optionally substituted non-aromatic heterocyclic ring.

[0151] A non-aromatic carbocycle refers to a ring whose ring constituent atoms are solely carbon atoms that are not aromatic throughout the ring. The non-aromatic carbocycle may be a monocyclic non-aromatic carbocycle or a polycyclic non-aromatic carbocycle. The non-aromatic carbocycle may be a saturated carbocycle consisting of only single bonds, or an unsaturated carbocycle having a double bond in addition to a single bond. The non-aromatic carbocycle is preferably a 3- to 21-membered non-aromatic carbocycle, more preferably a 4- to 18-membered non-aromatic carbocycle, and even more preferably a 5- to 14-membered non-aromatic carbocycle. Specific preferred examples of the non-aromatic carbocycle include monocyclic saturated carbocycles such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, and a cyclododecane ring; bicyclic saturated carbocycles such as a bicyclo[2.2.1]heptane ring (norbornane ring), a bicyclo[4.4.0]decane ring (decalin ring), a bicyclo[5.3.0]decane ring, a bicyclo[4.3.0]nonane ring (hydrindane ring), a bicyclo[3.2.1]octane ring, a bicyclo[5.4.0]undecane ring, a bicyclo[3.3.0]octane ring, and a bicyclo[3.3.1]nonane ring; 2,6] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7 ] Decane ring (adamantane ring), tricyclo[6.2.1.0 2,7 ]undecane ring and other saturated tricyclic carbocyclic rings.

[0152] A non-aromatic heterocycle refers to a ring that does not have aromaticity throughout the ring and has heteroatoms such as oxygen, nitrogen, and sulfur atoms in addition to carbon atoms as ring-constituting atoms. The non-aromatic heterocycle may be a monocyclic non-aromatic heterocycle or a polycyclic non-aromatic heterocycle. The non-aromatic heterocycle may be a saturated heterocycle consisting of only a single bond, or an unsaturated heterocycle having a double bond in addition to a single bond. The non-aromatic heterocycle is preferably a 3- to 21-membered non-aromatic heterocycle, more preferably a 4- to 18-membered non-aromatic heterocycle, and even more preferably a 5- to 14-membered non-aromatic heterocycle. Specific examples of suitable non-aromatic heterocycles include a 1,3-dioxane ring, a 1,3-dioxolane ring, a tetrahydropyran ring, and a tetrahydrofuran ring.

[0153] In one embodiment, ring A is preferably a non-aromatic carbocycle optionally substituted with an alkyl group or a non-aromatic heterocycle optionally substituted with an alkyl group; more preferably a tetrahydrodicyclopentadiene ring optionally substituted with an alkyl group or a 1,3-dioxane ring optionally substituted with an alkyl group.

[0154] In the second embodiment, the radical reactive group equivalent of the resin (B3) having a radical reactive group is preferably 30 g / eq. to 400 g / eq., more preferably 50 g / eq. to 300 g / eq., and even more preferably 75 g / eq. to 200 g / eq.

[0155] The molecular weight of the resin (B3) having a radical reactive group in the second embodiment is preferably 100-700, more preferably 200-400, and even more preferably 250-500.

[0156] In the third embodiment, the resin (B3) having a radical reactive group is preferably a resin represented by formula (5′):

[0157] [ka]

[0158] [In the formula, Ring B represents an optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring; i and j each independently represent an integer of 0 or 1 or greater, and the sum of i and j is 6 or greater; * indicates the binding site.] The maleimide compound includes a maleimide compound having a partial structure represented by the following formula: The maleimide compound refers to a compound containing at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) in one molecule. The number of maleimide groups in one molecule of the maleimide compound in the third embodiment is preferably 2 or more, and particularly preferably 2. The maleimide compound in the third embodiment may be used alone or in combination of two or more at any ratio.

[0159] The "substituent" in ring B of formula (5') is R A Examples of the substituents are the same as those in the above.

[0160] The monocycloalkane ring refers to a monocyclic aliphatic saturated hydrocarbon ring. The monocycloalkane ring is preferably a monocycloalkane ring having 4 to 14 carbon atoms, more preferably a monocycloalkane ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkane ring having 5 or 6 carbon atoms. Examples of the monocycloalkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. The monocycloalkene ring refers to a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The monocycloalkene ring is preferably a monocycloalkene ring having 4 to 14 carbon atoms, more preferably a monocycloalkene ring having 4 to 10 carbon atoms, and particularly preferably a monocycloalkene ring having 5 or 6 carbon atoms. Examples of the monocycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, and a cyclohexadiene ring.

[0161] Ring B represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent. Ring B is preferably a monocycloalkane ring which may have a substituent selected from an alkyl group and an alkenyl group; or a monocycloalkene ring which may have a group selected from an alkyl group and an alkenyl group. Ring B is more preferably a monocycloalkane ring which may have a substituent selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms; or a monocycloalkene ring which may have a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 2 to 14 carbon atoms.

[0162] i and j each independently represent an integer of 0 or 1 or more, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j are preferably each independently an integer of 0 to 20, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j are more preferably each independently an integer of 1 to 20, and the sum of i and j is 6 or more (preferably 8 or more, more preferably 10 or more). i and j are further preferably each independently an integer of 5 to 10. i and j are particularly preferably 8.

[0163] In the third embodiment, the resin (B3) having a radical reactive group is particularly preferably a resin represented by formula (5):

[0164] [ka]

[0165] [In the formula, R 10 each independently represents a substituent; ring C independently represents an aromatic ring which may have a substituent; D 1 and D 2 are each independently a single bond, -C(R x )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; R x each independently represents a hydrogen atom or an alkyl group; c's each independently represent 0 or 1; Each d independently represents an integer of 0 or 1 or more; e each independently represents 0, 1, or 2; n represents an integer of 0 or 1 or more; Other symbols are as above.] The d unit, the e unit, and the n unit may be the same or different for each unit.

[0166] R in Equation (5) 10 and the "substituent" in ring C include R A Examples of the substituents are the same as those in the above.

[0167] Each ring C independently represents an aromatic ring which may have a substituent, and is preferably a benzene ring which may have a substituent selected from alkyl groups. 1 and D 2 are each independently a single bond, -C(R x )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and preferably represents a single bond, -C(R x )2- or -O-. x are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. c are each independently 0 or 1, preferably 0. d are each independently an integer of 0 or 1 or more, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2. e are each independently 0, 1 or 2, preferably 0. n are each independently an integer of 0 or 1 or more, preferably 0.

[0168] Formula (D) contained in formula (5):

[0169] [ka]

[0170] [In the formula, * indicates a binding site; other symbols are as defined above.] The partial structure represented by the formula (D-1) to (D-3):

[0171] [ka]

[0172] [In the formula, * is the same as above.] Examples of the partial structure include:

[0173] The radical reactive group equivalent of the (B3) resin having a radical reactive group in the third embodiment is preferably 200 g / eq. to 2500 g / eq., more preferably 250 g / eq. to 2000 g / eq., and even more preferably 300 g / eq. to 1500 g / eq. The radical reactive group equivalent of the (B3) resin having a radical reactive group represents the mass of the resin per equivalent of the radical reactive group.

[0174] The weight average molecular weight of the resin (B3) having a radical reactive group in the third embodiment is preferably 400 to 10,000, more preferably 500 to 7,000, and particularly preferably 600 to 5,000.

[0175] Commercially available resins having a radical reactive group (B3) in the third embodiment include, for example, "BMI-689," "BMI-1500," "BMI-1700," and "BMI-3000J" manufactured by Designer Molecules, Inc., and "SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd.

[0176] In the fourth embodiment, the resin (B3) having a radical reactive group is preferably a resin represented by formula (6):

[0177] [ka]

[0178] [In the formula, R 20 each independently represents a hydrogen atom or an alkyl group; Ring E, ring F, and ring G each independently represent an aromatic ring which may have a substituent; Z 1 are each independently a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R z each independently represents a hydrogen atom or an alkyl group; f represents an integer equal to or greater than 1; g's each independently represent 0 or 1; Each h independently represents 0, 1, 2, or 3. The f units and h units may be the same or different for each unit. The maleimide compounds in the fourth embodiment may be used singly or in combination of two or more types in any ratio.

[0179] The "substituents" in ring E, ring F and ring G of formula (6) include R A Examples of the substituents are the same as those in the above.

[0180] R 20 are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0181] Ring E, ring F, and ring G each independently represent an aromatic ring which may have a substituent, preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group, and particularly preferably an (unsubstituted) benzene ring.

[0182] Z 1 are each independently a single bond, -C(R z )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, and preferably a single bond. z each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

[0183] f represents an integer of 1 or more, and preferably an integer of 1 to 10. g's each independently represent 0 or 1, and preferably 1. h's each independently represent 0, 1, 2, or 3, and preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 1.

[0184] The radical reactive group equivalent of the resin (B3) having a radical reactive group in the fourth embodiment is preferably 150 g / eq. to 1000 g / eq., and more preferably 200 g / eq. to 500 g / eq.

[0185] The weight average molecular weight of the resin (B3) having a radical reactive group in the fourth embodiment is preferably 100 to 10,000, more preferably 150 to 5,000, and particularly preferably 200 to 3,000.

[0186] Commercially available resins having a radical reactive group (B3) in the fourth embodiment include, for example, "MIR-3000-70MT" and "MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd.

[0187] In the fifth embodiment, the resin (B3) having a radical reactive group is preferably a resin represented by formula (7):

[0188] [ka]

[0189] [In the formula, R 30 each independently represents an alkyl group; Ring H and ring I each independently represent an aromatic ring which may have a substituent; m represents an integer of 1 or greater. The m units may be the same or different for each unit. The maleimide compounds in the fifth embodiment may be used singly or in combination of two or more types in any ratio.

[0190] The "substituents" in ring H and ring I of formula (7) include R A Examples of the substituents are the same as those in the above.

[0191] R 30 each independently represent an alkyl group, and in one embodiment, preferably a methyl group. Rings H each independently represent an aromatic ring which may have a substituent, and in one embodiment, preferably a benzene ring which may have a substituent, more preferably a benzene ring which may have a substituent selected from alkyl groups, and even more preferably a benzene ring substituted with a group selected from alkyl groups. Rings I each independently represent an aromatic ring which may have a substituent, and in one embodiment, preferably a benzene ring which may have a substituent, more preferably a benzene ring which may have a group selected from alkyl groups, and even more preferably an (unsubstituted) benzene ring. m represents an integer of 1 or more, and preferably an integer of 1 to 20.

[0192] The resin having a radical reactive group (B3) in the fifth embodiment can be produced, for example, by using the method described in the Journal of Technical Disclosure No. 2020-500211 of the Japan Institute of Invention and Innovation, or a method equivalent thereto.

[0193] (B3) The resin having a radical reactive group may contain any one of the preferred resins in the first embodiment, the preferred compounds in the second embodiment, the preferred compounds in the third embodiment, the preferred compounds in the fourth embodiment, and the preferred compounds in the fifth embodiment, alone, or may contain a combination of two or more of these in any ratio.

[0194] The radical reactive group equivalent of the (B3) resin having a radical reactive group is preferably 30 g / eq. to 2500 g / eq., particularly preferably 75 g / eq. to 2000 g / eq.

[0195] The content of (B3) resin having a radical reactive group in the resin composition is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of (B3) resin having a radical reactive group in the resin composition is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0196] The content of the (B) thermosetting resin in the resin composition is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (B) thermosetting resin in the resin composition is not particularly limited, but is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0197] The mass ratio of the thermosetting resin (B) to the polyimide resin (A) in the resin composition (component (B) / component (A)) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and particularly preferably 8 or more. The upper limit is not particularly limited, but is preferably 300 or less, more preferably 100 or less, and particularly preferably 30 or less.

[0198] <(C) Inorganic filler> The resin composition of the present invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the form of particles.

[0199] (C) Inorganic filler materials include inorganic compounds. Examples of (C) inorganic filler materials 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica, alumina, or aluminosilicate is preferred, with silica being particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred. The (C) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0200] (C) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30," "DAW-03," and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "Cellphears" and "MGH-005" manufactured by Taiheiyo Cement Corporation; and "Sferique" and "BA-1" manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0201] The average particle size of the (C) 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. The lower limit of the average particle size of the (C) 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. The average particle size of the (C) inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and ultrasonically dispersing for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution analyzer, with blue and red light source wavelengths used, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell system, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0202] The specific surface area of ​​the (C) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the inorganic filler (C) is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 50m 2 / g or less, more preferably 30m 2 / g or less, particularly preferably 10m 2 The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0203] The actual density of the inorganic filler can be measured using, for example, a true density measuring device. Examples of true density measuring devices include the Ultrapycnometer 1000 manufactured by Quantachrome. Nitrogen, for example, is used as the measurement gas.

[0204] The (C) inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent. The surface treatment agent may be used alone or in any combination of two or more.

[0205] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0206] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. 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 0.2% to 3% by mass, and even more preferably 0.3% to 2% by mass.

[0207] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1.0 mg / m 2 Less than 0.8 mg / m is preferred 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0208] (C) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. An "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used as the carbon analyzer.

[0209] The content of the (C) inorganic filler in the resin composition is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 65% ​​by mass or more, or 70% by mass or more, where the upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, particularly preferably 75% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0210] The mass ratio of the inorganic filler (C) to the polyimide resin (A) in the resin composition (component (C) / component (A)) is not particularly limited, but is preferably 2 or more, more preferably 10 or more, and particularly preferably 20 or more, and the upper limit is preferably 1000 or less, more preferably 300 or less, and particularly preferably 100 or less.

[0211] <(D) Curing accelerator> The resin composition of the present invention may further contain (D) a curing accelerator as an optional component. The (D) curing accelerator is a component that does not fall under the category of the (A) polyimide resin or the (B) thermosetting resin described above. The (D) curing accelerator functions as a curing catalyst that accelerates the curing of the (B) thermosetting resin.

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

[0213] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium bromide. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine aromatic phosphines such as benzene, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether;

[0214] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as toluene bis(dimethylurea), 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0215] Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0216] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and other imidazole compounds, as well as adducts of imidazole compounds with epoxy resins.

[0217] As the imidazole-based curing accelerator, commercially available products may be used, such as "1B2PZ", "2MZA-PW", "2PHZ-PW", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0218] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

[0220] As the amine-based curing accelerator, commercially available products may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0221] The content of (D) curing accelerator in the resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of (D) curing accelerator in the resin composition is not particularly limited, but may be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition.

[0222] <(E) Radical Polymerization Initiator> The resin composition of the present invention may contain (E) a radical polymerization initiator as an optional component. The (E) radical polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals upon heating. The (E) radical polymerization initiator may be a polymerization initiator of a radical reactive group. The (E) radical polymerization initiator may be used alone or in any combination of two or more types.

[0223] (E) Examples of the radical polymerization initiator include peroxide radical polymerization initiators, azo radical polymerization initiators, etc. Among these, peroxide radical polymerization initiators are preferred.

[0224] Examples of the peroxide radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide 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 diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydicarbonate. peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl) 2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, and tert-butylperoxymaleic acid; and the like.

[0225] Examples of the azo radical polymerization initiator 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-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, and 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile; 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]. azoamide compounds such as 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); alkyl azo compounds such as 2,2'-azobis(2,4,4-trimethylpentane) and 2,2'-azobis(2-methylpropane); and the like.

[0226] (E) Commercially available radical polymerization initiators include, for example, "Perbutyl C," "Perbutyl A," "Perbutyl P," "Perbutyl L," "Perbutyl O," "Perbutyl ND," "Perbutyl Z," "Perbutyl I," "Percumyl P," "Percumyl D," "Perhexyl D," "Perhexyl A," "Perhexyl I," "Perhexyl Z," "Perhexyl ND," "Perhexyl O," and "Perhexyl PV," all manufactured by NOF Corporation.

[0227] The content of the (E) radical polymerization initiator in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 5% by mass or less, more preferably 2% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. The lower limit may be, for example, 0% by mass or more, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.03% by mass or more.

[0228] <(F) Other additives> The resin composition of the present invention may further contain any additives. Examples of such additives include thermoplastic resins such as phenoxy resins; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silanes; triazole-based adhesion promoters and tetrazole-based adhesion promoters. Examples of the additives include adhesion promoters such as adhesion promoters and triazine-based adhesion promoters; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, and 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 anhydride-based stabilizers. (F) Other additives may be used singly or in combination of two or more in any ratio. (F) The content of other additives can be appropriately determined by a person skilled in the art.

[0229] <(G) Organic Solvent> The resin composition of the present invention may further contain an arbitrary organic solvent. (G) Organic solvents may be appropriately used, and the type is not particularly limited. (G) Organic solvents include, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol-based 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 of suitable organic solvents include ether ester solvents such as methyl ether, 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. The organic solvent (G) may be used singly or in combination of two or more solvents in any ratio.

[0230] The content of (G) organic solvent in the varnish-like resin composition before drying is not particularly limited, but is, for example, 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, when all components in the resin composition are taken as 100% by mass. The content of (G) organic solvent in the resin composition after drying to form a resin composition layer in a resin sheet is not particularly limited, but is, when all components in the resin composition are taken as 100% by mass, 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.

[0231] <Method of manufacturing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) polyimide resin, (B) thermosetting resin, (C) inorganic filler, optionally (D) curing accelerator, optionally (E) radical polymerization initiator, optionally (F) other additives, and optionally (G) organic solvent to any preparation vessel in any order and / or simultaneously in part or in whole, and mixing them. Furthermore, the temperature can be appropriately set during the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout the process. Furthermore, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse the resin composition. Furthermore, degassing may be performed under low-pressure conditions, such as under vacuum, simultaneously with the stirring or shaking.

[0232] <Characteristics of resin composition> The resin composition of the present invention comprises (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, wherein the polyimide resin (A) comprises a polyimide resin having one or more groups represented by the above-described formula (1) in each molecule. Such a resin composition can provide a cured product with a low dielectric loss tangent and good bending resistance.

[0233] The cured product of the resin composition of the present invention has excellent bending resistance, and therefore, when subjected to an MIT folding endurance test as in Test Example 3 below, the number of folding times that can be endured is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, and particularly preferably 250 or more.

[0234] A cured product of the resin composition of the present invention may be characterized by a low dielectric loss tangent. Thus, for example, the dielectric loss tangent (Df) of the cured product of the resin composition measured at 5.8 GHz and 23°C as in Test Example 2 below is not particularly limited, but may be preferably 0.020 or less, more preferably 0.010 or less, even more preferably 0.007 or less, still more preferably 0.005 or less, particularly preferably 0.004 or less, and particularly preferably 0.003 or less.

[0235] In one embodiment, the cured product of the resin composition of the present invention may be characterized by excellent peel strength of the plated conductor layer. Thus, in one embodiment, for example, as in the following Test Example 1, a copper plating conductor layer is formed on the cured product, and the copper plating peel strength calculated from the load when the copper plating conductor layer is peeled off in the vertical direction may be preferably 0.2 kgf / cm or more, more preferably 0.25 kgf / cm or more, even more preferably 0.30 kgf / cm or more, 0.35 kgf / cm or more, and particularly preferably 0.40 kgf / cm or more, 0.45 kgf / cm or more.

[0236] In one embodiment, the cured product of the resin composition of the present invention may be characterized by excellent strength. Thus, in one embodiment, for example, as in Test Example 4 below, when a 1 mm diameter needle is pierced into the cured product at 23°C at a rate of 50 mm / min, the strength at break may be preferably 0.6 N or more, more preferably 0.8 N or more, even more preferably 1.0 N or more, and particularly preferably 1.2 N or more.

[0237] <Applications of resin composition> 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 an insulating layer (resin composition for forming an insulating layer) for forming a conductor layer (including a rewiring layer) formed on the insulating 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 below. The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins.

[0238] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulating layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) 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 off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0239] Furthermore, the resin composition of the present invention provides an insulating layer with good component embedding properties, and therefore can be suitably used when the printed wiring board is a circuit board with built-in components.

[0240] <Sheet-type laminated material> The resin composition of the present invention can be used by applying it in the form of a varnish, but industrially it is generally preferred to use it in the form of a sheet-like laminate material containing the resin composition.

[0241] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0242] In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

[0243] 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 wiring board and providing a cured product of the resin composition with excellent insulating properties even when the cured product is thin. 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.

[0244] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0245] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0246] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0247] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0248] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent 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 also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0249] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0250] In one embodiment, the resin sheet may further include an optional layer as needed. Examples of such optional layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite 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, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0251] The resin sheet can be produced, for example, by preparing a liquid (varnish) resin composition as is or by dissolving the resin composition in an organic solvent, applying the liquid (varnish) resin composition onto a support using a die coater or the like, and then drying the applied composition to form a resin composition layer.

[0252] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0253] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition, for example, when a resin composition containing 30% by mass to 60% by mass of organic solvent is used, a resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0254] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0255] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0256] The sheet-like fiber 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 wiring board, the thickness of the sheet-like fiber 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 fiber substrate is not particularly limited. It is usually 10 μm or more.

[0257] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0258] The thickness of the prepreg may be in the same range as that of the resin composition layer in the resin sheet described above.

[0259] The sheet-like laminate material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

[0260] <Printed wiring board> The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0261] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer.

[0262] The "inner layer substrate" used in step (I) is a member that will become the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board." Furthermore, the "inner layer substrate" of the present invention also includes intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0263] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS end plate) or a metal roll (SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0264] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0265] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0266] After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0267] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0268] In step (II), the resin composition layer is cured (for example, by heat curing) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions typically employed for forming insulating layers for printed wiring boards may be used.

[0269] 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 is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0270] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0271] When manufacturing a printed wiring board, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art and used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be performed 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) to (V) may be repeated to form a multilayer wiring board.

[0272] In another embodiment, the printed wiring board of the present invention can be produced using the above-mentioned prepreg. The production method is basically the same as when a resin sheet is used.

[0273] 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 performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the printed wiring board.

[0274] Step (IV) is a step of roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The roughening treatment procedure and conditions are not particularly limited, and known procedures and conditions commonly used in forming insulating layers for printed wiring boards can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0275] The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions and surfactant solutions, and is preferably an alkaline solution, with sodium hydroxide solution and potassium hydroxide solution being more preferred. Commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be carried out by, for example, immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes. To keep the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0276] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as 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. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0277] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

[0278] Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the standpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0279] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after the 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 may be, for example, 1 nm or more, 2 nm or more, etc. Furthermore, the root mean square roughness (Rq) of the insulating layer surface after the 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 may 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.

[0280] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0281] The conductor layer may have a single layer structure or 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 conductor layer has 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 a nickel-chromium alloy.

[0282] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0283] 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 a conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by a semi-additive method will be described below.

[0284] First, a plating seed layer is formed on the surface of an 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 a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern.

[0285] In another embodiment, the conductor layer may be formed using a metal foil. When a metal foil is used to form the conductor layer, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil may be laminated 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. Thereafter, a conductor layer having a desired wiring pattern can be formed using the metal foil on the insulating layer by a conventionally known technique such as a subtractive method or a modified semi-additive method.

[0286] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0287] <Semiconductor device> The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0288] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0289] The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature conditions are room temperature (23°C), and unless otherwise specified, the pressure conditions are atmospheric pressure (1 atm).

[0290] [Synthesis Example 1: Synthesis of Polyimide Resin 1 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 46.5 g of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 50.4 g of 4,4'-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine (BPPAN), 1.9 g of 5-norbornene-2,3-dicarboxylic anhydride, and 40 g of toluene into 400 g of N,N-dimethylacetamide (DMAc) was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution.

[0291] The resulting polyamic acid solution was heated and then maintained at approximately 160°C, during which condensed water was azeotropically removed with toluene under a nitrogen stream. It was confirmed that the specified amount of water had accumulated in the water content receiver and that no water was leaking out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. It was then cooled. This yielded a varnish containing 20% ​​by mass of polyimide resin 1 as a non-volatile component.

[0292] [Synthesis Example 2: Synthesis of Polyimide Resin 2 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 46.5 g of BPADA, 37.8 g of BPPAN, 12.8 g of dimer diamine (PRIAMINE 1075), 1.9 g of 5-norbornene-2,3-dicarboxylic anhydride, and 40 g of toluene into 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 2 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0293] [Synthesis Example 3: Synthesis of Polyimide Resin 3 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 46.5 g of BPADA, 12.6 g of BPPAN, 38.3 g of dimer diamine (PRIAMINE 1075), 1.9 g of 5-norbornene-2,3-dicarboxylic anhydride, and 40 g of toluene as a solvent in 400 g of DMAc as a solvent was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 3 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0294] [Synthesis Example 4: Synthesis of Polyimide Resin 4 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 26.3 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as "BPDA"), 37.8 g of BPPAN, 12.8 g of dimer diamine (PRIAMINE 1075), 1.9 g of 5-norbornene-2,3-dicarboxylic anhydride, and 40 g of toluene into 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 4 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0295] [Synthesis Example 5: Synthesis of Polyimide Resin 5 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 27.7 g of 4,4'-oxydiphthalic anhydride (hereinafter also referred to as "ODPA"), 37.8 g of BPPAN, 12.8 g of dimer diamine (PRIAMINE 1075), 1.9 g of 5-norbornene-2,3-dicarboxylic anhydride, and 40 g of toluene into 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 5 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0296] [Synthesis Example 6: Synthesis of Polyimide Resin 6 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 46.5 g of BPADA, 37.8 g of BPPAN, 12.8 g of dimer diamine (PRIAMINE 1075), 1.8 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride, and 40 g of toluene into 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 6 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0297] [Synthesis Example 7: Synthesis of Polyimide Resin 7 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 26.3 g of BPDA, 29.4 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter also referred to as "BAPP"), 12.8 g of dimer diamine (PRIAMINE 1075), 1.8 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride, and 40 g of toluene into 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 7 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0298] [Synthesis Example 8: Synthesis of Polyimide Resin 8 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 46.5 g of BPADA, 12.6 g of BPPAN, 12.2 g of isophoronediamine (hereinafter also referred to as "IPDA"), 1.8 g of cis-4-cyclohexene-1,2-dicarboxylic anhydride, and 40 g of toluene into 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 8 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0299] [Synthesis Example 9: Synthesis of Polyimide Resin 9 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 26.3 g of BPDA, 29.4 g of BAPP, 12.8 g of dimer diamine (PRIAMINE 1075), 1.6 g of allyl succinic anhydride, and 40 g of toluene as a solvent in 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 9 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0300] [Synthesis Example 10: Synthesis of Polyimide Resin 10 (Terminal Olefin Modified)] A monomer mixture obtained by mixing 26.3 g of BPDA, 9.8 g of BAPP, 38.3 g of dimer diamine (PRIAMINE 1075), 1.6 g of allyl succinic anhydride, and 40 g of toluene in 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 10 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0301] [Synthesis Example 11: Synthesis of Polyimide Resin 11 (Unmodified)] A monomer mixture obtained by mixing 49.6 g of BPADA, 50.4 g of BPPAN, and 40 g of toluene in 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass % of polyimide resin 11 as a nonvolatile component was obtained in the same manner as in Synthesis Example 1.

[0302] [Synthesis Example 12: Synthesis of Polyimide Resin 12 (Terminal Maleimide Modified)] A monomer mixture obtained by mixing 46.5 g of BPADA, 50.4 g of BPPAN, 1.1 g of maleic anhydride, and 40 g of toluene into 400 g of DMAc was stirred and reacted at room temperature and atmospheric pressure for 3 hours. This resulted in a polyamic acid solution. Using the resulting polyamic acid solution, a varnish containing 20 mass% of polyimide resin 12 as a non-volatile component was obtained in the same manner as in Synthesis Example 1.

[0303] The raw materials and amounts used for synthesizing the polyimide resins of each synthesis example, as well as the number average molecular weight and weight average molecular weight (polystyrene equivalent) measured by gel permeation chromatography (GPC) are summarized in Table 1 below.

[0304] [Table 1]

[0305] [Example 1. Preparation of Resin Composition 1] Eight parts of a naphthalene-type epoxy resin ("HP4032SS" manufactured by DIC Corporation, epoxy equivalent weight: approximately 144 g / eq.) and 15 parts of a biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: approximately 290 g / eq.) were heated and dissolved in 20 parts of toluene and 20 parts of MEK while stirring. The resulting solution was cooled to room temperature and then mixed with 42 parts of an active ester-based curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, active group equivalent weight: 238 g / eq., toluene solution with a solid content of 62% by mass), 4 parts of a triazine skeleton-containing phenol-based curing agent ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent weight: approximately 151 g / eq., 2-methoxypropanol solution with a solid content of 50%), and the polyisoprene resin synthesized in Synthesis Example 1. Ten parts of imide resin 1 (solution with a solid content of 20% by mass), 3 parts of a curing accelerator (a MEK solution with a solid content of 10% of "1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.), and 150 parts of an inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) were mixed and uniformly dispersed in a high-speed rotating mixer to obtain resin composition 1.

[0306] [Example 2. Preparation of resin composition 2] Resin composition 2 was obtained in the same manner as in Example 1, except that 10 parts of polyimide resin 1 (solution with 20% solids by mass) synthesized in Synthesis Example 1 was replaced with 10 parts of polyimide resin 2 (solution with 20% solids by mass) synthesized in Synthesis Example 2.

[0307] [Example 3. Preparation of resin composition 3] Resin composition 3 was obtained in the same manner as in Example 2, except that 6 parts of a carbodiimide curing agent ("V-03" manufactured by Nisshinbo Chemical Inc., active group equivalent weight approximately 216 g / eq., toluene solution with a solid content of 50%) was further added.

[0308] [Example 4. Preparation of resin composition 4] Resin composition 4 was obtained in the same manner as in Example 2, except that 4.6 parts of a modified oligophenylene ether resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc., a toluene solution with a solid content of 65%) and 0.1 parts of a thermal radical generator ("Perbutyl D" manufactured by NOF Corporation) were added.

[0309] [Example 5. Preparation of Resin Composition 5] Resin composition 5 was obtained in the same manner as in Example 2, except that 3 parts of a bismaleimide resin ("BMI1500" manufactured by Designer Molecules, maleimide group equivalent weight: approximately 752 g / eq.) was added.

[0310] [Example 6. Preparation of resin composition 6] Resin composition 6 was obtained in the same manner as in Example 3, except that in Example 3, 42 parts of an active ester curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, active group equivalent 238 g / eq., toluene solution with a solid content of 62% by mass) was changed to 40 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq., toluene solution with a solid content of 65% by mass) and 10 parts of polyimide resin 2 synthesized in Synthesis example 2 (solution with a solid content of 20% by mass) was changed to 30 parts.

[0311] [Example 7. Preparation of Resin Composition 7] Resin composition 7 was obtained in the same manner as in Example 3, except that 10 parts of polyimide resin 2 (solution with 20% solids by mass) synthesized in Synthesis Example 2 was replaced with 10 parts of polyimide resin 3 (solution with 20% solids by mass) synthesized in Synthesis Example 3.

[0312] [Example 8. Preparation of resin composition 8] Resin composition 8 was obtained in the same manner as in Example 1, except that in Example 1, 42 parts of the active ester curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, active group equivalent 238 g / eq., toluene solution with a solid content of 62% by mass) was changed to 40 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq., toluene solution with a solid content of 65% by mass), and 10 parts of polyimide resin 1 synthesized in Synthesis Example 1 (solution with a solid content of 20% by mass) was changed to 10 parts of polyimide resin 4 synthesized in Synthesis Example 4 (solution with a solid content of 20% by mass).

[0313] [Example 9. Preparation of Resin Composition 9] Resin composition 9 was obtained in the same manner as in Example 1, except that in Example 1, 42 parts of the active ester curing agent ("HP-B-8151-62T" manufactured by DIC Corporation, active group equivalent 238 g / eq., toluene solution with a solid content of 62% by mass) was changed to 40 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent 223 g / eq., toluene solution with a solid content of 65% by mass), and 10 parts of polyimide resin 1 synthesized in Synthesis example 1 (solution with a solid content of 20% by mass) was changed to 10 parts of polyimide resin 5 synthesized in Synthesis example 5 (solution with a solid content of 20% by mass).

[0314] [Example 10. Preparation of resin composition 10] Resin composition 10 was obtained in the same manner as in Example 1, except that 10 parts of polyimide resin 1 (solution with 20% solids by mass) synthesized in Synthesis Example 1 was replaced with 10 parts of polyimide resin 6 (solution with 20% solids by mass) synthesized in Synthesis Example 6.

[0315] [Example 11. Preparation of Resin Composition 11] Resin composition 11 was obtained in the same manner as in Example 1, except that 10 parts of polyimide resin 1 (solution with 20% solids by mass) synthesized in Synthesis Example 1 was replaced with 10 parts of polyimide resin 7 (solution with 20% solids by mass) synthesized in Synthesis Example 7.

[0316] [Example 12. Preparation of resin composition 12] Resin composition 12 was obtained in the same manner as in Example 1, except that 10 parts of polyimide resin 1 (solution with 20% solids by mass) synthesized in Synthesis Example 1 was replaced with 10 parts of polyimide resin 8 (solution with 20% solids by mass) synthesized in Synthesis Example 8.

[0317] [Example 13. Preparation of resin composition 13] Resin composition 13 was obtained in the same manner as in Example 1, except that 10 parts of polyimide resin 1 (solution with 20% solids by mass) synthesized in Synthesis Example 1 was replaced with 10 parts of polyimide resin 9 (solution with 20% solids by mass) synthesized in Synthesis Example 9.

[0318] [Example 14. Preparation of resin composition 14] 70 parts of biphenylaralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent weight approx. 275 g / eq., MEK / toluene mixed solution with 70% non-volatile content), bismaleimide resin (Designer 10 parts of "BMI689" manufactured by Shin-Nakamura Chemical Co., Ltd. (maleimide group equivalent weight: approximately 345 g / eq.), 5 parts of a bifunctional acrylate ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 326 g / eq.), 30 parts of polyimide resin 4 (solution with 20% solids content by mass) synthesized in Synthesis Example 4, 0.7 parts of a thermal radical generator ("Perbutyl D" manufactured by NOF Corporation), 150 parts of an inorganic filler (spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and 20 parts of toluene were mixed and uniformly dispersed using a high-speed rotary mixer to obtain resin composition 14.

[0319] [Example 15. Preparation of resin composition 15] Resin composition 15 was obtained in the same manner as in Example 1, except that 10 parts of polyimide resin 1 (solution with 20% solids by mass) synthesized in Synthesis Example 1 was changed to 10 parts of polyimide resin 10 (solution with 20% solids by mass) synthesized in Synthesis Example 10.

[0320] Comparative Example 1: Preparation of Resin Composition 1' Resin composition 1' was obtained in the same manner as in Example 1, except that 10 parts of polyimide resin 1 (solution with 20% solids by mass) synthesized in Synthesis Example 1 was replaced with 10 parts of polyimide resin 11 (solution with 20% solids by mass) synthesized in Synthesis Example 11.

[0321] Comparative Example 2: Preparation of Resin Composition 2' Resin composition 2' was obtained in the same manner as in Example 1, except that 10 parts of polyimide resin 1 (solution with 20% solids by mass) synthesized in Synthesis Example 1 was replaced with 10 parts of polyimide resin 12 (solution with 20% solids by mass) synthesized in Synthesis Example 12.

[0322] Comparative Example 3: Preparation of Resin Composition 3' In Example 14, resin composition 3' was obtained in the same manner as in Example 14, except that 30 parts of polyimide resin 4 (solution with 20% solids by mass) synthesized in Synthesis Example 4 was replaced with 30 parts of polyimide resin 11 (solution with 20% solids by mass) synthesized in Synthesis Example 11.

[0323] [Test Example 1. Measurement of peel strength of plated conductor layer] (1) Preparation of resin sheet As a support, a polyethylene terephthalate film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130° C.) that had been subjected to a release treatment with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) was prepared.

[0324] The resin compositions obtained in the examples and comparative examples were each uniformly applied to a support using a die coater so that the thickness of the dried resin composition layer was 40 μm, and then dried at 70 to 95° C. for 4 minutes to form a resin composition layer on the support. Next, the rough surface of a polypropylene film (Oji F-Tex Co., Ltd., "Alphan MA-411", thickness 15 μm) was attached as a protective film to the side of the resin composition layer that was not bonded to the support. This resulted in a resin sheet A having a support, a resin composition layer, and a protective film in this order.

[0325] (2) Preparation of inner layer board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with an inner layer circuit formed on it were etched 1 μm deep with a microetching agent (MEC "CZ8101") to roughen the copper surface.

[0326] (3) Laminating resin sheets The protective film was peeled off from Resin Sheet A to expose the resin composition layer. Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700"), the resin composition layer was laminated onto both sides of the inner layer substrate so that it was in contact with the inner layer substrate. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, followed by pressure bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0327] (4) Thermal curing of the resin composition layer The inner layer substrate laminated with the resin sheet was then placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 180°C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. The support was then peeled off to obtain a cured substrate A having the insulating layer, inner layer substrate, and insulating layer in this order.

[0328] (5) Roughening treatment A desmear treatment as a roughening treatment was performed on the cured substrate A. The desmear treatment was the following wet desmear treatment. (wet desmear treatment) Cured substrate A was immersed in a swelling solution (Atotech Japan's "Swelling Dip Securigant P," an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then in an oxidizing solution (Atotech Japan's "Concentrate Compact CP," an aqueous solution of potassium permanganate at approximately 6% and sodium hydroxide at approximately 4%) at 80°C for 15 minutes, and then in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P," an aqueous sulfuric acid solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

[0329] (6) Formation of the conductor layer A conductor layer was formed on the roughened surface of the insulating layer using a semi-additive process. Specifically, the roughened substrate was immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, and then in an electroless copper plating solution at 25°C for 20 minutes. Next, the substrate was heated at 150°C for 30 minutes for annealing, after which an etching resist was formed and a pattern was formed by etching. Copper sulfate electroplating was then performed to form a 30 μm-thick conductor layer, which was then annealed at 200°C for 60 minutes. The resulting substrate is referred to as "Evaluation Substrate B."

[0330] (7) Measurement of peel strength of plated conductor layer The peel strength of the insulating layer and conductor layer was measured in accordance with the Japanese Industrial Standard (JIS C6481). Specifically, a 10 mm wide and 100 mm long notch was made in the conductor layer of evaluation board B, one end of which was peeled off and gripped with a gripper. The peel strength was determined by measuring the load (kgf / cm) when 35 mm was peeled off vertically at a rate of 50 mm / min at room temperature (23°C). A tensile tester (TSE "AC-50C-SL") was used for the measurement.

[0331] [Test Example 2. Measurement of dielectric loss tangent] The protective film was removed from the same resin sheet A as that obtained in Test Example 1(1), and the resin composition layer was thermally cured by heating at 200°C for 90 minutes, after which the support was peeled off. The obtained cured product is referred to as "evaluation cured product C." The evaluation cured product C was cut into a test piece measuring 2 mm in width and 80 mm in length. The dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C using an "HP8362B" manufactured by Agilent Technologies by the cavity resonance perturbation method. Measurements were performed on three test pieces, and the average value was calculated.

[0332] [Test Example 3. Measurement of MIT folding endurance] A cured product for evaluation C similar to that obtained in Test Example 2 was cut into test pieces 15 mm wide and 110 mm long, and a bending test was carried out using an MIT testing device (MIT folding fatigue tester "MIT-DA" manufactured by Toyo Seiki Seisaku-sho, Ltd.) under the measurement conditions of a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / min. Cured products for evaluation that were bent 250 times or more before breaking were evaluated as "◎", those that were bent 150 times or more but less than 250 times were evaluated as "◯", and those that were bent less than 150 times were evaluated as "×".

[0333] [Test Example 4. Measurement of puncture strength] Cured product C for evaluation, similar to that obtained in Test Example 2, was cut into test pieces 400 mm wide and 400 mm long and fixed to a film puncture test jig with a hole diameter of 20 mm. Using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.), a needle with a diameter of 1 mm was punctured at a rate of 50 mm / min at room temperature (23°C), and the strength at break was measured.

[0334] The non-volatile components and amounts used of the resin compositions of the Examples and Comparative Examples, the measurement results of the test examples, and the evaluation results are summarized in Table 2 below.

[0335] [Table 2]

[0336] The results shown in Table 2 above show that by using a resin composition containing (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, in which the polyimide resin (A) has one or more groups represented by the above-described formula (1) in one molecule, it is possible to obtain a cured product having a low dielectric tangent and good bending resistance.

Claims

1. A resin composition comprising (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, The component (A) is represented by the formula (1): 【Chemistry 1】 [In the formula, (i) R １ and R ２ each independently represents a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and R １ and R ２ at least one of is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group, or (ii) R １ and R ２ are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; * indicates the binding site. However, the divalent hydrocarbon group is a divalent unsaturated hydrocarbon group having one or more carbon atoms as skeletal atoms and hydrogen atoms as non-skeletal atoms, and bonding to one atom via a non-aromatic double bond.] The polyimide resin contains one or more groups represented by the following formula (I): The component (B) contains an epoxy resin (B1) and an active ester curing agent, A resin composition, wherein the content of the active ester-based curing agent is 1% by mass or more, when the total amount of non-volatile components in the resin composition is 100% by mass.

2. A resin composition comprising (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, The component (A) is represented by the formula (2): 【Chemistry 2】 [In the formula, X's each independently represent a divalent organic group consisting of five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; Y's each independently represent a tetravalent organic group having five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms, and having an aromatic ring; (i) R 1 and R 2 each independently represent a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and at least one of R 1 and R 2 is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group; or (ii) R 1 and R 2 are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; n represents the average number of repeating units, which is 1 or more. However, the divalent hydrocarbon group is a divalent unsaturated hydrocarbon group having one or more carbon atoms as skeletal atoms and hydrogen atoms as non-skeletal atoms, and bonding to one atom via a non-aromatic double bond.] The polyimide resin is represented by A resin composition, wherein, when n+1 X's are 100 mol%, 1 mol% to 80 mol% of them are divalent organic groups having no aromatic ring, and 20 mol% to 99 mol% of them are divalent organic groups having an aromatic ring.

3. A resin composition comprising (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, The component (A) is represented by the formula (1): 【Transformation 3】 [In the formula, (i) R １ and R ２ each independently represents a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and R １ and R ２ at least one of is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group, or (ii) R １ and R ２ are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; * indicates the binding site. However, the divalent hydrocarbon group is a divalent unsaturated hydrocarbon group having one or more carbon atoms as skeletal atoms and hydrogen atoms as non-skeletal atoms, and bonding to one atom via a non-aromatic double bond.] The polyimide resin contains one or more groups represented by the following formula (I): The component (B) contains an epoxy resin (B1) and a phenolic curing agent, A resin composition, wherein the content of the phenolic curing agent is 5% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass.

4. A resin composition comprising (A) a polyimide resin, (B) a thermosetting resin, and (C) an inorganic filler, The component (A) is represented by the formula (1): 【Chemistry 4】 [In the formula, (i) R １ and R ２ each independently represents a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and R １ and R ２ at least one of is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group, or (ii) R １ and R ２ are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; * indicates the binding site. However, the divalent hydrocarbon group is a divalent unsaturated hydrocarbon group having one or more carbon atoms as skeletal atoms and hydrogen atoms as non-skeletal atoms, and bonding to one atom via a non-aromatic double bond.] The polyimide resin contains one or more groups represented by the following formula (I): the component (C) is treated with at least one surface treatment agent selected from the group consisting of a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent; A resin composition, wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 5 to 100.

5. A resin composition as described in claim 1, wherein component (B) further contains a phenolic curing agent.

6. A resin composition as described in claim 5, wherein the content of the phenolic curing agent is 5 mass% or less when the non-volatile components in the resin composition are 100 mass%.

7. The component (A) is represented by the formula (2): 【Transformation 5】 [In the formula, X's each independently represent a divalent organic group consisting of five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; Y's each independently represent a tetravalent organic group consisting of five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms; (i) R １ and R ２ each independently represents a hydrogen atom, a monovalent hydrocarbon group, or a divalent hydrocarbon group, and R １ and R ２ at least one of is a monovalent ethylenically unsaturated bond-containing hydrocarbon group or a divalent hydrocarbon group, or (ii) R １ and R ２ are bonded together to form an ethylenically unsaturated bond-containing carbocyclic ring optionally substituted with a monovalent hydrocarbon group, or an ethylenically unsaturated bond-containing heterocyclic ring optionally substituted with a monovalent hydrocarbon group; n represents the average number of repeating units of 1 or more. The resin composition according to claim 1, comprising a polyimide resin represented by the formula:

8. The resin composition according to claim 7, wherein X is a divalent organic group consisting of five or more skeletal atoms selected from carbon, oxygen, and sulfur atoms and non-skeletal atoms selected from hydrogen and halogen atoms, and when n+1 Xs are taken as 100 mol%, 1 mol% to 80 mol% of them are divalent organic groups without an aromatic ring, and 20 mol% to 99 mol% are divalent organic groups with an aromatic ring.

9. 8. The resin composition according to claim 7, wherein each Y is independently a tetravalent organic group having five or more skeletal atoms selected from carbon atoms, oxygen atoms, and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms, and having an aromatic ring.

10. The resin composition according to claim 1, wherein the content of the component (A) is 5% by mass or less, based on 100% by mass of nonvolatile components in the resin composition.

11. The resin composition according to claim 1, wherein the weight average molecular weight of component (A) is 10,000 or more.

12. The resin composition according to claim 2, wherein the component (B) comprises an epoxy resin (B1).

13. The resin composition according to claim 2, wherein the component (B) comprises an epoxy resin curing agent (B2).

14. The resin composition according to claim 13, wherein the component (B2) comprises an active ester-based curing agent.

15. The resin composition according to claim 13, wherein the component (B2) comprises a phenol-based curing agent.

16. The resin composition according to claim 2 , wherein the component (B) comprises (B3) a resin having a radical reactive group.

17. 2. The resin composition according to claim 1, wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 5 to 100.

18. The resin composition according to claim 1, wherein the content of the component (C) is 50% by mass or more, based on 100% by mass of nonvolatile components in the resin composition.

19. The resin composition according to claim 1, wherein the dielectric loss tangent (Df) of a cured product of the resin composition is 0.003 or less when measured at 5.8 GHz and 23°C.

20. The resin composition according to claim 1, which is used to form an insulating layer of a semiconductor chip package.

21. A cured product of the resin composition according to any one of claims 1 to 20.

22. A resin sheet comprising: a support; and a resin composition layer formed on the support from the resin composition according to any one of claims 1 to 20.

23. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 19.

24. A semiconductor device comprising the printed wiring board according to claim 23.

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