Resin composition

Abstract

To provide a resin composition that can yield a cured product having low relative dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition point (Tg), and excellent copper adhesion.SOLUTION: Provided is a resin composition that contains (A) a maleimide compound having a partial structure represented by the formula (A) (X1) (in the formula, each symbol is as described in the specification), and (B) an active ester compound.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

[0003] So far, various maleimide compounds containing non-aromatic ring skeletons have been known (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a resin composition capable of obtaining a cured product having a low relative dielectric constant (Dk), a low dielectric tangent (Df), a high glass transition point (Tg), and excellent copper adhesion.

Means for Solving the Problems

[0006] In order to achieve the object of the present invention, the inventors of the present invention have conducted intensive studies. As a result, by using, as components of the resin composition, (A) a maleimide compound having a partial structure represented by the formula (X1) and (B) an active ester compound, surprisingly, a cured product having a low relative permittivity (Dk) and a low dielectric loss tangent (Df), a high glass transition temperature (Tg), and excellent copper adhesion can be obtained. Based on this finding, the present invention has been completed.

[0007] That is, the present invention includes the following. [1] A resin composition containing (A) a maleimide compound having a partial structure represented by the formula (X1):

[0008] [Chemical formula]

[0009] [In the formula, ring X represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; a and b each independently represent 0, 1, 2, or 3, and the sum of a and b is 1 to 5; * represents a bonding site.] and (B) an active ester compound. [2] The resin composition according to [1] above, wherein the component (A) is a maleimide compound having, in addition to the partial structure represented by the formula (X1), a partial structure represented by the formula (Y1):

[0010] [Chemical formula]

[0011] [In the formula, ring Y represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; c and d each independently represent 0 or an integer of 1 or more, and the sum of c and d is 6 or more; * represents a bonding site.] ​ [3] The resin composition according to [1] or [2] above, wherein the number of maleimide groups in the molecule of component (A) is 2. [4] The resin composition according to any one of [1] to [3] above, wherein component (A) is a maleimide-terminated polyimide. [5] Component (A) is represented by the formula (A1):

[0012] [Chemical formula]

[0013] [In the formula, R 1 each independently represents a substituent; ring X and ring Y each independently represent a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; ring Z each independently represents a non-aromatic ring which may have a substituent or an aromatic ring which may have a substituent; Z 1 and Z 2 each independently represent a single bond, an alkylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; a and b each independently represent 0, 1, 2 or 3, and the sum of a and b is 1 to 5; c and d each independently represent 0 or an integer of 1 or more, and the sum of c and d is 6 or more; e each independently represents 0 or 1; f each independently represents 0 or an integer of 1 or more; g each independently represents 0, 1 or 2; n1 represents an integer of 1 or more; n2 represents 0 or an integer of 1 or more; m1 and m2 are such that one of them represents 1 and the other represents 0.] The resin composition according to any one of [1] to [4] above, which is a compound represented by the formula. The resin composition according to any one of [1] to [5] above, wherein the weight average molecular weight of component (A) is 2,000 to 50,000. [7] The resin composition according to any one of [1] to [6] above, wherein the content of component (A) is 3% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass. [8] The resin composition according to any one of [1] to [7] above, wherein the content of component (B) is 3% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass. [9] The resin composition according to any one of [1] to [8] above, wherein the mass ratio of component (A) to component (B) ((A) component / (B) component) is 0.5 to 3.

[10] The resin composition according to any one of [1] to [9] above, further comprising (C) an epoxy resin.

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

[10] above, further comprising (D) an inorganic filler.

[12] The resin composition according to

[11] above, wherein the content of component (D) is 40% by mass or more when the non-volatile components in the resin composition are 100% by mass.

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

[12] above, wherein the dielectric tangent (Df) of the cured product of the resin composition is 0.005 or less when measured at 5.8 GHz and 23°C.

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

[13] above, wherein the relative dielectric constant (Dk) of the cured product of the resin composition is 3.0 or less when measured at 5.8 GHz and 23°C.

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

[14] above, wherein the glass transition temperature (Tg) of the cured product of the resin composition is 150°C or higher.

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

[15] above.

[17] A sheet-like laminated material containing the resin composition according to any one of [1] to

[15] above.

[18] A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of [1] to

[15] above provided on the support.

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

[15] above.

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

[19] above. [Advantages of the Invention]

[0014] According to the resin composition of the present invention, a cured product having a low relative permittivity (Dk) and a low dielectric loss tangent (Df), a high glass transition temperature (Tg), and excellent copper adhesion can be obtained. [Embodiments for Carrying Out the Invention]

[0015] Hereinafter, the present invention will be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and exemplifications, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0016] [Resin Composition] The resin composition of the present invention contains (A) a maleimide compound represented by the formula (X1):

[0017] [Chemical Formula]

[0018] [In the formula, ring X represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; a and b each independently represent 0, 1, 2 or 3, and the sum of a and b is 1 to 5; * represents a bonding site.] and (B) an active ester compound. By using such a resin composition, a cured product having a low relative permittivity (Dk) and a low dielectric loss tangent (Df), a high glass transition temperature (Tg), and excellent copper adhesion can be obtained.

[0019] The resin composition of the present invention may further contain optional components in addition to (A) a specific maleimide compound and (B) an active ester compound. Examples of the optional components include, for example, (A') other radically polymerizable compounds, (C) an epoxy resin, (D) an inorganic filler, (E) a curing accelerator, (F) other additives, and (G) an organic solvent. Hereinafter, each component contained in the resin composition will be described in detail.

[0020] <(A) Specific maleimide compound> The resin composition of the present invention contains (A) a specific maleimide compound. The maleimide compound means 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 (A) the specific maleimide compound is preferably 2 or more, and particularly preferably 2. (A) The specific maleimide compound may be used alone or in combination of two or more in any ratio.

[0021] (A) The specific maleimide compound has the formula (X1):

[0022]

Chemical formula

[0023] [In the formula, ring X represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent; a and b each independently represent 0, 1, 2 or 3, and the sum of a and b is 1 to 5; * represents a bonding site.] has a partial structure represented by.

[0024] Ring X represents a monocycloalkane ring which may have a substituent, or a monocycloalkene ring which may have a substituent.

[0025] A monocyclic alkane ring means a monocyclic aliphatic saturated hydrocarbon ring. The monocyclic alkane ring is preferably a monocyclic alkane ring having 4 to 14 carbon atoms, more preferably a monocyclic alkane ring having 4 to 10 carbon atoms, and particularly preferably a monocyclic alkane ring having 5 or 6 carbon atoms. Examples of the monocyclic alkane ring include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, etc. A cycloalkene ring means a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond. The monocyclic cycloalkene ring is preferably a monocyclic cycloalkene ring having 4 to 14 carbon atoms, more preferably a monocyclic cycloalkene ring having 4 to 10 carbon atoms, and particularly preferably a monocyclic cycloalkene ring having 5 or 6 carbon atoms. Examples of the monocyclic cycloalkene ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, a cyclohexadiene ring, etc.

[0026] In this specification, the "substituent" is not particularly limited, and examples thereof include monovalent substituents such as an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, etc. If substitution is possible, divalent substituents such as an oxo group (=O) may also be included.

[0027] An alkyl (group) means a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, an alkyl (group) having 1 to 14 carbon atoms is preferred. 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, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, etc. An alkenyl (group) means a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, an alkenyl group having 2 to 14 carbon atoms is preferred. Examples of the alkenyl (group) include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a cyclohexenyl group, etc. An aryl (group) means a monovalent aromatic hydrocarbon group. Unless otherwise specified, an aryl (group) having 6 to 14 carbon atoms is preferred. Examples of the aryl (group) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc.

[0028] Ring X is preferably a monocycloalkane ring which may be substituted with a group selected from an alkyl group and an alkenyl group, or a monocycloalkene ring which may be substituted with a group selected from an alkyl group and an alkenyl group. More preferably, ring X is a monocycloalkane ring having 4 to 10 carbon atoms which may be substituted with a group selected from an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 1 to 6 carbon atoms, or a monocycloalkene ring having 4 to 10 carbon atoms which may be substituted with a group selected from an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 1 to 6 carbon atoms. Even more preferably, ring X is a monocycloalkane ring having 4 to 10 carbon atoms which may be substituted with a group selected from an alkyl group having 1 to 6 carbon atoms. Particularly preferably, ring X is a cyclohexane ring which may be substituted with a methyl group.

[0029] a and b each independently represent 0, 1, 2 or 3, and the sum of a and b is 1 to 5. a and b are preferably each independently 0, 1 or 2, and the sum of a and b is 1 or more. a and b are more preferably each independently 0 or 1, and the sum of a and b is 1 or more. a and b are particularly preferably such that one of a and b is 1 and the other is 0.

[0030] The partial structure represented by formula (X1) is preferably formula (X2):

[0031]

Chemical formula

[0032] [In the formula, R 2 each independently represents an alkyl group; x represents an integer from 0 to 5; and the other symbols are the same as above.] is the partial structure represented by

[0033] R 2 each independently represents an alkyl group. R 2 each independently represents preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. x represents an integer from 0 to 5. x is preferably 0, 1, 2, 3 or 4, more preferably 1, 2, 3 or 4, still more preferably 2, 3 or 4, and particularly preferably 3.

[0034] The partial structure represented by formula (X1) is particularly preferably formula (X3):

[0035]

Chemical formula

[0036] [In the formula, * is the same as above.] is the partial structure represented by

[0037] (A) The number of the partial structures represented by the formula (X1) in one molecule of the specific maleimide compound is at least 1, preferably 2 or more, and the upper limit can be, for example, 20 or less, 10 or less, etc.

[0038] (A) The specific maleimide compound preferably further has, in addition to the partial structure represented by the formula (X1), the formula (Y1):

[0039]

Chemical formula

[0040] [In the formula, ring Y represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; c and d each independently represent 0 or an integer of 1 or more, and the sum of c and d is 6 or more; * represents a bonding site.] and has a partial structure represented by the following.

[0041] Ring Y represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent. Ring Y is preferably a monocycloalkane ring which may be substituted with a group selected from an alkyl group and an alkenyl group, or a monocycloalkene ring which may be substituted with a group selected from an alkyl group and an alkenyl group. Ring Y is more preferably a monocycloalkane ring having 4 to 10 carbon atoms which may be substituted with a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 1 to 14 carbon atoms, or a monocycloalkene ring having 4 to 10 carbon atoms which may be substituted with a group selected from an alkyl group having 1 to 14 carbon atoms and an alkenyl group having 1 to 14 carbon atoms. Ring Y is even more preferably a monocycloalkane ring having 4 to 10 carbon atoms which may be substituted with a group selected from an alkyl group having 1 to 14 carbon atoms. Ring Y is particularly preferably a cyclohexane ring which may be substituted with a group selected from an alkyl group having 4 to 10 carbon atoms.

[0042] c and d each independently represent an integer of 0 or 1 or more, and the sum of c and d is 6 or more. c and d are preferably each independently an integer from 0 to 20, and the sum of c and d is 6 or more. c and d are more preferably each independently an integer from 1 to 20, and the sum of c and d is 6 or more. c and d are even more preferably each independently an integer from 5 to 10. c and d are particularly preferably 8.

[0043] The partial structure represented by formula (Y1) is preferably formula (Y2):

[0044]

Chemical formula

[0045] [In the formula, R 3 each independently represents an alkyl group; y represents an integer from 0 to 5; and the other symbols are the same as above.] is the partial structure represented by the formula.

[0046] R 3 each independently represents an alkyl group. R 3 each independently represents, preferably, an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and particularly preferably an alkyl group having 6 to 8 carbon atoms. y represents an integer from 0 to 5. y is preferably 0, 1, 2, 3, or 4, more preferably 1, 2, 3, or 4, even more preferably 1, 2, or 3, and particularly preferably 2.

[0047] The partial structure represented by formula (Y1) is particularly preferably formula (Y3):

[0048]

Chemical formula

[0049] [In the formula, * is the same as above.] It is a partial structure represented by

[0050] (A) The number of partial structures represented by formula (Y1) in one molecule of the specific maleimide compound is at least 1, preferably 2 or more, and the upper limit can be, for example, 20 or less, 10 or less, etc.

[0051] (A) In one embodiment, the specific maleimide compound is preferably a maleimide-terminated polyimide. A maleimide-terminated polyimide is a chain polyimide having maleimide groups at both ends (a chain polymer containing an imide structure in the repeating unit). It is known that a maleimide-terminated polyimide can be obtained, for example, by subjecting a component containing a diamine compound, maleic anhydride, and a tetracarboxylic dianhydride to an imidization reaction.

[0052] (A) In one embodiment, the specific maleimide compound has the formula (n1):

[0053] [Chemical formula]

[0054] [In the formula, R 1 each independently represents a substituent; ring Z each independently represents a non-aromatic ring which may have a substituent or an aromatic ring which may have a substituent; Z 1 and Z 2 each independently represents a single bond, an alkylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; e each independently represents 0 or 1; f each independently represents 0 or an integer of 1 or more; g each independently represents 0, 1, or 2; and the other symbols are the same as above.] It is preferably a maleimide compound containing a structural unit represented by, and in addition to the structural unit represented by formula (n1), further has the formula (n2):

[0055] [Chemical formula]

[0056] [In the formula, each symbol is the same as described above.] It is more preferable that the maleimide compound contains a structural unit represented by. The f unit and the g unit may be the same or different for each unit.

[0057] R 1 each independently represents a substituent, preferably an alkyl group. Ring Z each independently represents a non-aromatic ring which may have a substituent or an aromatic ring which may have a substituent, preferably an aromatic ring which may have a substituent.

[0058] An aromatic ring means a ring that follows Hückel's rule where the number of electrons contained in the π electron system on the ring is 4p + 2 (p is a natural number). The aromatic ring can be an aromatic carbon ring having carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring having, in addition to carbon atoms, heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc. as ring-constituting atoms. However, in one embodiment, it is preferably an aromatic carbon ring. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 5- to 10-membered aromatic ring, and even more preferably a 5- or 6-membered aromatic ring. Preferable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc., more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

[0059] The non-aromatic ring means a ring other than an aromatic ring. The non-aromatic ring can be a non-aromatic carbocyclic ring having carbon atoms as ring-constituting atoms, or a non-aromatic heterocyclic ring having, in addition to carbon atoms, hetero atoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc. as ring-constituting atoms. However, in one embodiment, it is preferably a non-aromatic carbocyclic ring. The non-aromatic ring may be a saturated ring or an unsaturated non-aromatic ring, but in one embodiment, it is preferably a saturated ring. In one embodiment, the non-aromatic ring is preferably a 4- to 14-membered non-aromatic ring. Examples of the non-aromatic ring include monocycloalkane rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring; monocycloalkene rings such as cyclobutene ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, cyclooctene ring, cyclopentadiene ring, cyclohexadiene ring; aromatic ring-non-aromatic ring condensed rings such as indane ring, indene ring, tetralin ring, fluorene ring, etc.

[0060] Z 1 and Z 2 each independently represents a single bond, an alkylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-.

[0061] The alkylene group means a straight-chain or branched-chain divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms. Examples of the alkylene group include straight-chain alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group; branched-chain alkylene groups such as ethylidene group (-CH(CH3)-), propylidene group (-CH(CH2CH3)-), isopropylidene group (-C(CH3)2-), ethylmethylmethylene group (-C(CH3)(CH2CH3)-), diethylmethylene group (-C(CH2CH3)2-), etc.

[0062] e represents 0 or 1, preferably 0. f each independently represents 0 or an integer of 1 or more, preferably 0, 1 or 2. g each independently represents 0, 1 or 2, preferably 0.

[0063] The partial structure represented by formula (X1) included in the structural unit represented by formula (n1) is preferably the partial structure represented by formula (X2), and particularly preferably the partial structure represented by formula (X3). The partial structure represented by formula (Y1) included in the structural unit represented by formula (n2) is preferably the partial structure represented by formula (Y2), and particularly preferably the partial structure represented by formula (Y3).

[0064] The formula (Z) included in the structural units represented by formula (n1) and formula (n2):

[0065]

Chemical formula

[0066] [Wherein, * is the same as above.] Specific examples of the partial structure represented by are the formulas (Z-1) to (Z-25):

[0067]

Chemical formula

[0068] [Wherein, * is the same as above.] The partial structure represented by any of is exemplified, and among them, the partial structure represented by formula (Z-1) is preferable.

[0069] (A) In one embodiment, the specific maleimide compound is more preferably the formula (A1):

[0070]

Chemical formula

[0071] [In the formula, n1 represents an integer of 1 or more; n2 represents 0 or an integer of 1 or more (preferably an integer of 1 or more); either m1 or m2 represents 1 and the other represents 0; other symbols are the same as above.] It is a compound represented by (a bond between the n1 unit and the n2 unit). The order and individual arrangements of the n1 unit and the n2 unit are arbitrary and include alternating copolymers, block copolymers, random copolymers, etc. The n1 unit and the n2 unit may be the same or different for each unit.

[0072] The partial structure represented by the formula (X1) contained in the compound represented by the formula (A1) is preferably the partial structure represented by the formula (X2), and particularly preferably the partial structure represented by the formula (X3). The partial structure represented by the formula (Y1) contained in the compound represented by the formula (A1) is preferably the partial structure represented by the formula (Y2), and particularly preferably the partial structure represented by the formula (Y3). The partial structure represented by the formula (Z) contained in the compound represented by the formula (A1) is preferably the partial structure represented by the formula (Z-1).

[0073] (A) In one embodiment, the specific maleimide compound is more preferably the formula (A2):

[0074]

Chemical formula

[0075] [In the formula, each symbol is the same as above.] It is a compound represented by (a bond between the n1 unit and the n2 unit), and particularly preferably the formula (A3):

[0076]

Chemical formula

[0077] [In the formula, each symbol is the same as above.] It is a compound represented by (a bond between the n1 unit and the n2 unit).

[0078] (A) The weight average molecular weight (Mw) of the specific maleimide compound is preferably from 1,000 to 50,000, more preferably from 2,000 to 50,000, still more preferably from 2,000 to 40,000, and even more preferably from 2,500 to 20,000. (A) The number average molecular weight (Mn) of the specific maleimide compound is preferably from 1,000 to 50,000, more preferably from 1,500 to 40,000, and even more preferably from 2,000 to 20,000. The weight average molecular weight and the number average molecular weight of the resin can be measured as values in terms of polystyrene by the gel permeation chromatography (GPC) method.

[0079] (A) The functional group equivalent weight of the specific maleimide compound is preferably from 500 g / eq. to 20,000 g / eq., more preferably from 1,000 g / eq. to 10,000 g / eq. (A) The functional group equivalent weight of the specific maleimide compound is the mass of the specific maleimide compound per 1 equivalent of the maleimide group.

[0080] Examples of commercially available products of the (A) specific maleimide compound include "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd.

[0081] The content of the (A) specific maleimide compound in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. The lower limit of the content of the (A) specific maleimide compound in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more.

[0082] <(A') Other radically polymerizable compounds> The resin composition of the present invention may further contain, as an optional component, a (A') radically polymerizable compound other than the component (A). The (A') radically polymerizable compound may be used alone or in any combination of two or more.

[0083] (A') The radically polymerizable compound may be, for example, a compound having a radically polymerizable unsaturated group. The radically polymerizable unsaturated group is not particularly limited as long as it is radically polymerizable, but an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside is preferable. Specifically, unsaturated aliphatic groups such as allyl group and 3-cyclohexenyl group; unsaturated aliphatic group-containing aromatic groups such as p-vinylphenyl group, m-vinylphenyl group, and styryl group; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleoyl group (maleimide group when imidized), and fumaroyl group, etc. The (A') radically polymerizable compound preferably has one or more radically polymerizable unsaturated groups, and more preferably two or more.

[0084] (A') As other radically polymerizable compounds, known radically polymerizable compounds can be widely used and are not particularly limited. For example, maleimide-based radically polymerizable compounds having two or more maleimide groups other than the component (A), vinylphenyl-based radically polymerizable compounds having two or more vinylphenyl groups, (meth)acrylic-based radically polymerizable compounds having two or more acryloyl groups and / or methacryloyl groups, etc. can be mentioned.

[0085] The maleimide-based radically polymerizable compound is not particularly limited and may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available products include "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing a dimer diamine structure) manufactured by Designer Molecules, Inc., "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules, Inc., "MIR-5000-60T", "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) manufactured by Nippon Kayaku Co., Ltd., "BMI-70", "BMI-80" manufactured by Kay-Ichi Kasei Co., Ltd., "BMI-2300", "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd., and the like. Further, as the maleimide-based radically polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in Invention Association Public Technical Report Publication No. 2020-500211 may be used.

[0086] The vinylphenyl-based radically polymerizable compound is not particularly limited. However, in one embodiment, it is preferably a thermoplastic resin having a vinylphenyl group, and more preferably a resin selected from a modified polyphenylene ether resin having a vinylphenyl group and a modified polystyrene resin having a vinylphenyl group. Examples of commercially available products include "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Company, Inc.; "ODV-XET-X03", "ODV-XET-X04", "ODV-XET-X05" (divinylbenzene / styrene copolymer) manufactured by Nippon Steel Chemical & Material Co., Ltd., and the like.

[0087] (Meth)acrylic radical polymerizable compounds are not particularly limited, but in one embodiment, they are preferably thermoplastic resins having acryloyl groups and / or methacryloyl groups. Resins selected from modified polyphenylene ether resins having acryloyl groups and / or methacryloyl groups, and modified polystyrene resins having acryloyl groups and / or methacryloyl groups are more preferred. Commercially available products include, for example, "SA9000", "SA9000-111" (methacrylic modified polyphenylene ether resin) manufactured by SABIC Innovative Plastics.

[0088] (A’) The functional group equivalent weight of other radical polymerizable compounds is preferably 100 g / eq. to 20,000 g / eq., more preferably 200 g / eq. to 15,000 g / eq., and even more preferably 300 g / eq. to 10,000 g / eq. The functional group equivalent weight of other radical polymerizable compounds (A’) is the mass of other radical polymerizable compounds (A’) per equivalent of radical polymerizable unsaturated groups (i.e., maleimide groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, etc.).

[0089] (A’) The weight average molecular weight (Mw) of other radical polymerizable compounds is preferably 500 to 50,000, more preferably 700 to 20,000. The number average molecular weight (Mn) of other radical polymerizable compounds (A’) is preferably 500 to 50,000, more preferably 700 to 20,000.

[0090] The content of other radical polymerizable compounds (A’) in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of other radical polymerizable compounds (A’) in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it can be, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, etc.

[0091] When the content of the (A) specific maleimide compound in the resin composition is based on 100% by mass of the total radically polymerizable compounds ((A) component and (A') component) in the resin composition, it is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.

[0092] <(B) active ester compound> The resin composition of the present invention contains a (B) active ester compound. The (B) active ester compound may be used alone or in combination of two or more in any ratio. In one embodiment, when the resin composition contains a (C) epoxy resin or when the resin composition is mixed with a (C) epoxy resin, the (B) active ester compound may have a function as an epoxy resin curing agent that reacts with the (C) epoxy resin to cure it.

[0093] (B) As the active ester compound, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0094] Specifically, as the (B) active ester compound, a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, it is more preferably at least one selected from a dicyclopentadiene-type active ester compound and a naphthalene-type active ester compound, and a dicyclopentadiene-type active ester compound is even more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

[0095] As commercially available products of the (B) active ester compound, as the active ester compound containing a dicyclopentadiene-type diphenol structure, there are "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC); as the active ester compound containing a naphthalene structure, there are "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC); as the phosphorus-containing active ester compound, there is "EXB9401" (manufactured by DIC), as the active ester compound which is an acetylated product of phenol novolak, there is "DC808" (manufactured by Mitsubishi Chemical Corporation), as the active ester compound which is a benzoylated product of phenol novolak, there are "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and as the active ester compound containing a styryl group and a naphthalene structure, there is "PC1300-02-65MA" (manufactured by Air Water) and the like.

[0096] (B) The active ester group equivalent of the active ester compound is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., still more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

[0097] The content of the (B) active ester compound in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. The lower limit of the content of the (B) active ester compound in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more.

[0098] The mass ratio of the (A) specific maleimide compound to the (B) active ester compound in the resin composition ((A) component / (B) component) is preferably 0.1 or more, more preferably 0.5 or more, and particularly preferably 0.7 or more. The upper limit of the mass ratio of the (A) specific maleimide compound to the (B) active ester compound in the resin composition ((A) component / (B) component) is preferably 10 or less, more preferably 3 or less, and particularly preferably 1.5 or less.

[0099] <(C) epoxy resin> The resin composition of the present invention may contain (C) an epoxy resin as an optional component. The (C) epoxy resin is a curable resin having an epoxy group.

[0100] (C) Examples of the epoxy resin include novolac epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimide type epoxy resin, phenolphthalein type epoxy resin, etc. The (C) epoxy resin may be used alone or in combination of two or more.

[0101] The resin composition preferably contains, as the (C) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more based on 100% by mass of the non-volatile component of the (C) epoxy resin.

[0102] Epoxy resins include liquid epoxy resins (hereinafter sometimes referred to as "liquid epoxy resins") that are liquid at a temperature of 20°C and solid epoxy resins (hereinafter sometimes referred to as "solid epoxy resins") that are solid at a temperature of 20°C. The resin composition of the present invention may contain only a liquid epoxy resin as the epoxy resin, or may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin or a combination of a liquid epoxy resin and a solid epoxy resin, and more preferably a solid epoxy resin.

[0103] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0104] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferred.

[0105] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycerol-type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine-type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene-type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600", "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd., and the like. These may be used alone or in combination of two or more.

[0106] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0107] Examples of the solid epoxy resin include a biphenol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenylethane-type epoxy resin, a phenolphthalimide-type epoxy resin, and a phenolphthalein-type epoxy resin.

[0108] Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", and "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", 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; "YX7700" (phenol aralkyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like.These may be used alone or in combination of two or more.

[0109] (C) When using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin / solid epoxy resin) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, still more preferably 1 or less, even more preferably 0.5 or less, and particularly preferably 0.1 or less.

[0110] (C) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., still more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0111] (C) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC) method.

[0112] The content of the (C) epoxy resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The lower limit of the content of the (C) epoxy resin in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, for example, it is 0% by mass or more, preferably 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more.

[0113] The mass ratio of the (A) specific maleimide compound to the (C) epoxy resin in the resin composition ((A) component / (C) component) is preferably 0.1 or more, more preferably 0.3 or more, and particularly preferably 0.5 or more. The upper limit of the mass ratio of the (A) specific maleimide compound to the (C) epoxy resin in the resin composition ((A) component / (C) component) is preferably 10 or less, more preferably 3 or less, and particularly preferably 1 or less.

[0114] <(D) Inorganic filler> The resin composition of the present invention may contain a (D) inorganic filler as an optional component. The (D) inorganic filler is contained in the resin composition in a particulate state.

[0115] As the material of the (D) inorganic filler, an inorganic compound is used. Examples of the material of the (D) inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungsten phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Also, spherical silica is preferred as the silica. The (D) inorganic filler may be used alone or in combination of two or more in any ratio.

[0116] (D) Examples of commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03" and "FB-105FD" manufactured by Denka Co., Ltd., etc.

[0117] (D) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle size of the (D) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (D) inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter thereof is taken as the average particle size for measurement. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample can be used to measure the volume-based particle size distribution of the inorganic filler using a laser diffraction type particle size distribution measuring device with the wavelengths of the light sources used being blue and red and in a flow cell method, and the average particle size is calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0118] (D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 2 / g or more, particularly preferably 3 m 2 / g or more. (D) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 50 m 2 / g or less, particularly preferably 40 m 2 / g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multi-point method.

[0119] (D) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By being surface-treated, the moisture resistance and dispersibility of the (D) inorganic filler can be enhanced. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; methacryl-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; amino-based silane coupling agents such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; and other silane coupling agents.Examples of the alkylalkoxysilane compound include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane and the like. The surface treatment agent may be used alone or in combination of two or more thereof at an arbitrary ratio.;

[0120] Examples of the commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl-based silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy-based silane coupling agent); "KBM-1403" (styryl-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic-based silane coupling agent); "KBM-5103" (acrylic-based silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino-based silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (acid anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (alkylalkoxysilane compound) and the like.

[0121] From the perspective of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass, and even more preferably surface-treated with 0.3% to 2% by mass.

[0122] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the perspective of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and even more preferably 0.5 mg / m 2 or less.

[0123] (D) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. etc. can be used.

[0124] The content of the (D) inorganic filler in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, it can preferably be 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and particularly preferably 70% by mass or less. The lower limit of the content of the (D) inorganic filler in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, it can be, for example, 0% by mass or more, 1% by mass or more, etc., and can preferably be 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 50% by mass or more.

[0125] The mass ratio of the (A) specific maleimide compound to the (D) inorganic filler in the resin composition ((A) component / (D) component) is preferably 0.01 or more, more preferably 0.05 or more, and particularly preferably 0.1 or more. The upper limit of the mass ratio of the (A) specific maleimide compound to the (D) inorganic filler in the resin composition ((A) component / (D) component) is preferably 1 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less.

[0126] <(E) Curing accelerator> The resin composition of the present invention may contain an (E) curing accelerator as an optional component. In one embodiment, when the resin composition contains a (C) epoxy resin, or when the resin composition is mixed with a (C) epoxy resin, the (E) curing accelerator has a function of promoting the curing of the (C) epoxy resin.

[0127] Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. Among them, from the viewpoint of improving crosslinkability, imidazole-based curing accelerators are preferred. The (E) curing accelerator may be used alone or in combination of two or more.

[0128] Examples of phosphorus-based curing accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine;Aromatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenylether, etc. are mentioned.;

[0129] Examples of urea-based curing accelerators include, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea], and the like.

[0130] Examples of guanidine-based curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like.

[0131] Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

[0132] As the imidazole-based curing accelerator, commercially available products may be used. For example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Kogyo Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can be mentioned.

[0133] Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of the organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0134] Examples of the amine-based hardening 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.

[0135] As the amine-based hardening accelerator, commercially available products may be used. For example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc. may be mentioned.

[0136] The content of the hardening accelerator (E) in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The lower limit of the content of the hardening accelerator (E) in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are 100% by mass, it can be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, etc.

[0137] <(F) Other Additives> The resin composition of the present invention may further contain an optional additive as a non-volatile component. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; epoxy curing agents other than active ester compounds such as phenolic curing agents, acid anhydride-based curing agents, thiol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, imidazole-based curing agents, and amine-based curing agents; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic fillers such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as benton and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc.(F) Other additives may be used alone, or two or more of them may be combined and used in any ratio. (F) The content of other additives can be appropriately set by those skilled in the art.

[0138] <(G) Organic solvent> In addition to the non-volatile components described above, the resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component. (G) As the organic solvent, known ones can be appropriately used, and the type thereof is not particularly limited. (G) Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene, etc. (G) The organic solvent may be used alone or in combination of two or more in any ratio.

[0139] In one embodiment, the content of the (G) organic solvent is not particularly limited, but when the total components in the resin composition are 100% by mass, for example, it can be 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, etc.

[0140] <Method for producing resin composition> The resin composition of the present invention can be produced, for example, by adding (A) a specific maleimide compound, (B) an active ester compound, optionally (A') other radically polymerizable compounds, optionally (C) an epoxy resin, optionally (D) an inorganic filler, optionally (E) a curing accelerator, optionally (F) other additives, and optionally (G) an organic solvent to an arbitrary preparation container in an arbitrary order and / or partially or all at the same time and mixing them. Further, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or throughout the process. Further, in the process of adding and mixing or thereafter, the resin composition may be stirred or shaken using a stirring device such as a mixer or a shaking device to be uniformly dispersed. Further, defoaming may be performed under low pressure conditions such as under vacuum simultaneously with stirring or shaking.

[0141] <Properties of resin composition> The resin composition of the present invention contains (A) a specific maleimide compound and (B) an active ester compound. By using such a resin composition, a cured product having a low relative permittivity (Dk) and a low dielectric loss tangent (Df), a high glass transition temperature (Tg), and excellent copper adhesion can be obtained.

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

[0143] The cured product of the resin composition of the present invention may have a characteristic of low relative permittivity (Dk). Therefore, in one embodiment, the relative permittivity (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23°C as in Test Example 1 below may preferably be 5.0 or less, more preferably 4.0 or less, still more preferably 3.5 or less, and particularly preferably 3.0 or less.

[0144] The cured product of the resin composition of the present invention may have a characteristic of high glass transition temperature (Tg). Therefore, in one embodiment, the glass transition temperature (Tg) when measured as in Test Example 2 below may preferably be 120°C or higher, more preferably 140°C or higher, still more preferably 150°C or higher, and particularly preferably 160°C or higher.

[0145] The cured product of the resin composition of the present invention may have a characteristic of excellent copper adhesion. Therefore, in one embodiment, the adhesion strength of the underlying copper (copper foil) when measured in accordance with JIS C6481 as in Test Example 5 below may preferably be 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, still more preferably 0.4 kgf / cm or more, and particularly preferably 0.5 kgf / cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf / cm or less. Further, in one embodiment, the copper plating peel strength calculated from the load when forming a copper plating conductor layer on the cured product and peeling the copper plating conductor layer in the vertical direction as in Test Example 4 below may preferably be 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, still more preferably 0.35 kgf / cm or more, and particularly preferably 0.4 kgf / cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf / cm or less.

[0146] In one embodiment, the cured product of the resin composition of the present invention may have a feature that the arithmetic mean roughness (Ra) of the surface after the roughening treatment is low. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the surface of the cured product after the roughening treatment measured as in Test Example 3 below is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 170 nm or less, even more preferably 150 nm or less, and particularly preferably 130 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc.

[0147] <Use of the resin composition> The resin composition of the present invention can be suitably used as a resin composition for insulation applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. Also, in a printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of the printed wiring board (resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention can also be widely used in applications where a resin composition is required, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, etc.

[0148] Also, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a resin composition for a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring formation layer), and a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the encapsulation layer. (1) Step of laminating a temporary fixing film on a substrate, (2) Step of temporarily fixing a semiconductor chip on the temporary fixing film, (3) Step of forming an encapsulation layer on the semiconductor chip, (4) Step of peeling the base material and the temporary fixing film from the semiconductor chip (5) Step of forming a redistribution formation layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer

[0149] In addition, since the resin composition of the present invention provides an insulating layer with good component embedding properties, it can also be suitably used when the printed wiring board is a component-built-in circuit board.

[0150] <Sheet-like laminated material> The resin composition of the present invention can be used by being applied in a varnish state, but industrially, it is generally preferable to use it in the form of a sheet-like laminated material containing the resin composition.

[0151] As the sheet-like laminated material, the resin sheets and prepregs shown below are preferable.

[0152] 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.

[0153] From the viewpoints of thinning the printed wiring board and providing a cured product having excellent insulating properties even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but usually, it can be 5 μm or more, 10 μm or more, etc.

[0154] Examples of the support include a film made of a plastic material, a metal foil, and release paper, and a film made of a plastic material and a metal foil are preferable.

[0155] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), etc., polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0156] When using a metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0157] The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface that is joined to the resin composition layer.

[0158] In addition, as the support, a support with a release layer having a release layer on the surface joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. As the support with a release layer, commercially available products may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.

[0159] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When using a support with a release layer, it is preferable that the total thickness of the support with the release layer is within the above range.

[0160] In one embodiment, the resin sheet may further contain any layer as needed. Examples of such an arbitrary layer include a protective film similar to the support provided on the surface of the resin composition layer that is not joined to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and scratches to the surface of the resin composition layer.

[0161] The resin sheet can be produced, for example, by directly using a liquid resin composition or preparing a resin varnish by dissolving the resin composition in an organic solvent, applying this onto the support using a die coater or the like, and further drying to form a resin composition layer.

[0162] Examples of the organic solvent include the same ones as those described as components of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0163] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% to 60% by mass of the organic solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0164] The resin sheet can be stored by being wound into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0165] In one embodiment, the prepreg is formed by impregnating a sheet-shaped fiber base material with the resin composition of the present invention.

[0166] The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid 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-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

[0167] The prepreg can be produced by known methods such as the hot melt method and the solvent method.

[0168] The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

[0169] The sheet-shaped laminated material of the present invention can be suitably used for forming the insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used for forming the interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board).

[0170] <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.

[0171] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the resin sheet described above. (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of curing (for example, thermosetting) the resin composition layer to form an insulating layer

[0172] The "inner layer substrate" used in Process (I) is a member that serves as the substrate of a printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Further, the substrate may have a conductor layer on one or both sides, and this conductor layer may be pattern-processed. An inner layer substrate with a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Also, in the production of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "inner layer substrate" as referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate incorporating components may be used.

[0173] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). Note that it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate, rather than pressing the thermocompression bonding member directly against the resin sheet.

[0174] The lamination of the inner layer substrate and the resin sheet may be carried out by the vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C; the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa; and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under a reduced pressure condition of 26.7 hPa or less.

[0175] The lamination can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., the Vacuum Applicator manufactured by Nippon Materials Co., Ltd., and the batch type vacuum pressure laminator.

[0176] After lamination, under normal pressure (atmospheric pressure), for example, by pressing the heat-bonding member from the support side, a smoothing treatment of the laminated resin sheet may be performed. The pressing conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above lamination. The smoothing treatment can be performed by a commercially available laminator. Note that the lamination and the smoothing treatment may be continuously performed using the above commercially available vacuum laminator.

[0177] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0178] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0179] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition and the like. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and still more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

[0180] 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 still more preferably 15 minutes to 100 minutes.

[0181] When manufacturing a printed wiring board, the following steps may be further carried out: (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 carried out according to various methods known to those skilled in the art and used in the manufacture of printed wiring boards. When removing the support after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

[0182] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-described prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

[0183] Step (III) is a step of drilling holes in the insulating layer, by which holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0184] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also carried out in this step (IV). The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by carrying out 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.

[0185] The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution. Preferably, it is an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security P" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but for example, it can be performed by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0186] The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0187] Also, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0188] The treatment with the neutralizing liquid can be performed by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object that has been roughened with the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0189] In one embodiment, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0190] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0191] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0192] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0193] In one embodiment, the conductor layer may be formed by plating. For example, a plating seed layer can be formed on the surface of the insulating layer by a conventionally known technique such as the semi-additive method or the full-additive method to form a conductor layer having a desired wiring pattern. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0194] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0195] In another embodiment, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, it is preferably carried out between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as the subtractive method or the modified semi-additive method.

[0196] The metal foil can be manufactured by a known method such as the electrolytic method or the rolling method. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., and the like.

[0197] <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.

[0198] Examples of the semiconductor device include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes, etc.).

Example

[0199] Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "mass%", respectively, unless otherwise specified. The temperature conditions and pressure conditions in the case where the temperature and pressure are not specified are room temperature (23°C) and atmospheric pressure (1 atm).

[0200] <Example 1> 20 parts of a maleimide compound containing an isophoronediamine skeleton ("SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., an anisole solution with a solid content of 50% by mass, main component (non-volatile component): a maleimide compound represented by the following formula (A)), 17.7 parts of an active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, a toluene solution with a solid content of 62% by mass), 18 parts of a naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd.), spherical silica surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm, specific surface area 5.8 m 2 / g) 60 parts, 1 part of an imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Chemicals Corporation, 1-benzyl-2-phenylimidazole), and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin composition (resin varnish).

[0201]

Chemical formula

[0202] <Example 2> The amount of the active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with a solid content of 62% by mass) was changed from 17.7 parts to 16.1 parts, and the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd.) was changed from 18 parts to 15 parts. A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 5.7 parts of a biphenyl aralkyl novolak type polymaleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK / toluene mixed solution with a solid content of 70%) was further used.

[0203] <Example 3> A MEK solution (non-volatile component: 70% by mass) of a maleimide compound A represented by the following formula (1) (Mw / Mn = 1.81, t’’ = 1.47 (mainly 1, 2 or 3)) synthesized by the method described in Synthesis Example 1 of Publication No. 2020-500211 of the Technical Report of the Japan Institute of Invention was prepared.

[0204]

Chemical formula

[0205] The amount of the active ester compound ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with a solid content of 62% by mass) was changed from 17.7 parts to 16.1 parts, and the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd.) was changed from 18 parts to 15 parts. A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 5.7 parts of the maleimide compound A (MEK solution with a solid content of 70%) was further used.

[0206] <Example 4> The amount of the active ester compound ("HPC-8150-62T" manufactured by DIC, toluene solution with a solid content of 62% by mass) was changed from 17.7 parts to 16.1 parts, the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd.) was changed from 18 parts to 15 parts, and 6.2 parts of a terminal vinyl benzylated PPE compound ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, toluene mixed solution with a solid content of 65%) was further used. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0207] <Example 5> The amount of the active ester compound ("HPC-8150-62T" manufactured by DIC, toluene solution with a solid content of 62% by mass) was changed from 17.7 parts to 16.1 parts, the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd.) was changed from 18 parts to 15 parts, and 6.2 parts of a divinylbenzene / styrene copolymer ("ODV-XET-X04" manufactured by Nippon Steel Chemical & Material Co., Ltd., toluene solution with a solid content of 65%) was further used. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0208] <Example 6> The amount of the active ester compound ("HPC-8150-62T" manufactured by DIC, toluene solution with a solid content of 62% by mass) was changed from 17.7 parts to 16.1 parts, the amount of the naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd.) was changed from 18 parts to 15 parts, and 8 parts of a terminal methacryl-modified PPE compound ("SA9000-111" manufactured by SABIC Innovative Plastics, adjusted to a 50% solid content solution in toluene) was further used. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0209] <Comparative Example 1> Instead of 20 parts of an isophoronediamine skeleton-containing maleimide compound ("SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd.), 10 parts of an aliphatic maleimide ("BMI-689" manufactured by Designer Molecules, Inc.) was used. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0210] <Comparative Example 2> Instead of 20 parts of the isophoronediamine skeleton-containing maleimide compound (“SLK-2600” manufactured by Shin-Etsu Chemical Co., Ltd.), 14.3 parts of a biphenyl aralkyl novolak type polymaleimide (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with a solid content of 70%) was used, and a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0211] <Comparative Example 3> Without using 20 parts of the isophoronediamine skeleton-containing maleimide compound (“SLK-2600” manufactured by Shin-Etsu Chemical Co., Ltd.), the amount of the active ester compound (“HPC-8150-62T” manufactured by DIC Corporation, a toluene solution with a solid content of 62% by mass) was changed from 17.7 parts to 25.8 parts, and the amount of the naphthol aralkyl type epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical & Material Co., Ltd.) was changed from 18 parts to 23 parts. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0212] <Comparative Example 4> Without using 17.7 parts of the active ester compound (“HPC-8150-62T” manufactured by DIC Corporation, a toluene solution with a solid content of 62% by mass), the amount of the spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 60 parts to 51 parts, and 8.3 parts of a phenolic epoxy curing agent (“LA-7054” manufactured by DIC Corporation, a MEK solution with a solid content of 60%) was further used. Otherwise, a resin composition (resin varnish) was prepared in the same manner as in Example 1.

[0213] <Test Example 1: Measurement of Relative Dielectric Constant (Dk) and Dissipation Factor (Df)> As the support, a polyethylene terephthalate film having a release layer (「AL5」manufactured by Lintec Corporation, thickness 38 μm) was prepared. On the release layer of this support, the resin compositions obtained in the examples and comparative examples were uniformly coated so that the thickness of the resin composition layer after drying would be 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A including the support and the resin composition layer.

[0214] The obtained resin sheet A was cured in an oven at 190°C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained. The cured product was cut into pieces with a length of 80 mm and a width of 2 mm to obtain a cured product B for evaluation.

[0215] Regarding the cured product B for evaluation, using 「HP8362B」manufactured by Agilent Technologies, the value of the dielectric constant (Dk value) and the value of the dielectric tangent (Df value) were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity resonance perturbation method. The measurement was carried out with two test pieces, and the average was calculated.

[0216] <Test Example 2: Measurement of Glass Transition Temperature (Tg)> The resin sheet A obtained in Test Example 1 was cured in an oven at 190°C for 90 minutes, and further peeled off from the support to obtain a cured film. This cured film was cut into pieces with a length of 20 mm and a width of 6 mm to obtain an evaluation sample. Regarding this evaluation sample, using a TMA device (thermal mechanical analyzer) manufactured by Rigaku, the glass transition temperature (Tg) was measured at a heating rate of 5°C / min from 25°C to 250°C. The same test piece was measured twice, and the value of the second measurement was recorded.

[0217] <Test Example 3: Measurement of Arithmetic Mean Roughness (Ra)> (1) Preparation of Inner Layer Substrate Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, 「R1515A」manufactured by Panasonic Corporation) on which an inner layer circuit was formed were etched with a micro-etching agent (「CZ8101」manufactured by Meck) by 1 μm for roughening the copper surface.

[0218] (2) Lamination of Resin Sheet A Using a batch-type vacuum pressure laminator (manufactured by Nippon Materials Co., Ltd., two-stage build-up laminator "CVP700"), the resin sheet A obtained in Test Example 1 was laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by adjusting the air pressure to 13 hPa or less by decompression for 30 seconds and then crimping at 120 °C and a pressure of 0.74 MPa for 30 seconds. Subsequently, a hot press was performed at 100 °C and a pressure of 0.5 MPa for 60 seconds.

[0219] (3) Thermal curing of the resin composition layer Thereafter, the inner layer substrate laminated with the resin sheet A was put into an oven at 130 °C and heated for 30 minutes, and then transferred to an oven at 170 °C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate, and an insulating layer in this order.

[0220] (4) Roughening treatment A desmear treatment as a roughening treatment was performed on the cured substrate A. As the desmear treatment, the following wet desmear treatment was carried out.

[0221] (Wet desmear treatment) The cured substrate A was immersed in a swelling solution (manufactured by Atotech Japan Co., Ltd. "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 °C for 5 minutes, and then immersed in an oxidizing agent solution (manufactured by Atotech Japan Co., Ltd. "Concentrate Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 °C for 20 minutes. Subsequently, it was immersed in a neutralizing solution (manufactured by Atotech Japan Co., Ltd. "Reduction Solution Securigant P", an aqueous sulfuric acid solution) at 40 °C for 5 minutes and then dried at 80 °C for 15 minutes.

[0222] (5) Measurement of the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment The arithmetic mean roughness (Ra) of the surface of the insulating layer of the cured substrate A after roughening treatment was determined by the numerical values obtained with a non-contact surface roughness meter (WYKO NT3300 manufactured by Bruker) in VSI mode and a 50x lens with a measurement range of 121 μm × 92 μm. The measurement was performed by obtaining the average value of 10 points each.

[0223] <Test Example 4: Measurement of Copper Plating Peel Strength> (1) Formation of Copper Plated Conductor Layer According to the semi-additive method, a conductor layer was formed on the roughened surface of the insulating layer of the cured substrate A obtained in Test Example 3. That is, the substrate after roughening treatment was immersed in an electroless plating solution containing PdCl2 at 40 °C for 5 minutes, and then immersed in an electroless copper plating solution at 25 °C for 20 minutes. Next, after annealing treatment by heating at 150 °C for 30 minutes, an etching resist was formed, and patterning was performed by etching. Thereafter, electrolytic copper plating was performed to form a conductor layer with a thickness of 25 μm, and annealing treatment was performed at 190 °C for 60 minutes. The obtained substrate is referred to as "Evaluation Substrate B".

[0224] (2) Measurement of Peel Strength of Copper Plated Conductor Layer The measurement of the peel strength between the insulating layer and the conductor layer was carried out in accordance with Japanese Industrial Standard (JIS C6481). Specifically, a cut was made in a 10 mm wide and 100 mm long portion of the conductor layer of Evaluation Substrate B, one end of this was peeled off and grasped with a gripping tool, and the load (kgf / cm) when peeling 35 mm vertically at a speed of 50 mm / min at room temperature was measured to obtain the peel strength. A tensile testing machine ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[0225] <Test Example 5: Measurement of Adhesion Strength of Underlying Copper (Copper Foil)> (1) Underlying Treatment of Copper Foil The shiny surface of "3EC-III" (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. was immersed in a micro-etching agent ("CZ8101" manufactured by Meck Co., Ltd.) to perform roughening treatment (Ra value = 1 μm) on the copper surface, and rust prevention treatment (CL8300) was applied. This copper foil is referred to as CZ copper foil. Furthermore, heat treatment was performed in an oven at 130 °C for 30 minutes.

[0226] (2) Lamination of Copper Foil and Formation of Insulating Layer An inner layer substrate laminated with Resin Sheet A was prepared in the same manner as in Test Example 3. Thereafter, the supports on both sides were peeled off from the substrate to expose the resin composition layers on both sides. The treated surface of the CZ copper foil of "3EC-III" was laminated on these resin composition layers under the same conditions as the lamination of Resin Sheet A in Test Example 1. Then, the resin composition layer was cured under the curing conditions of 190 °C for 90 minutes to form an insulating layer, thereby producing a sample.

[0227] (3) Measurement of Copper Foil Peel Strength (Adhesion to Substrate) The produced sample was cut into small pieces of 150×30 mm. A cut was made in the copper foil portion of the small piece with a width of 10 mm and a length of 100 mm using a cutter, and one end of the copper foil was peeled off and grasped with a gripping tool ("AC-50C-SL" manufactured by TSE Co., Ltd.). The load [kgf / cm (N / cm)] when peeling 35 mm vertically at a speed of 50 mm / min at room temperature was measured in accordance with JIS C6481 using an Instron universal testing machine.

[0228] The usage amounts of the non-volatile components of the resin compositions in the examples and comparative examples and the measurement results of the test examples are shown in Table 1 below.

[0229]

Table 1

[0230] Referring to Table 1, in Comparative Examples 2 and 3 that do not use a specific maleimide compound, the copper foil adhesion is low, and the relative dielectric constant (Dk) and the dissipation factor (Df) are high values. Further, in Comparative Example 1 that uses a maleimide compound composed of a dimer diamine skeleton instead of the (A) specific maleimide compound, the glass transition temperature (Tg) is a low value. In Comparative Example 4 that uses a phenolic curing agent instead of the (B) active ester compound as the epoxy curing agent, the relative dielectric constant (Dk) and the dissipation factor (Df) are extremely high values. On the other hand, it can be seen that when the resin composition of the present invention containing the (A) specific maleimide compound and the (B) active ester compound is used, these problems can be overcome.

Claims

1. (A) Compound (X1): 【Chemical 1】 [wherein ring X represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; a and b each independently represent 0, 1, 2 or 3, and the sum of a and b is 1 to 5; * represents a bonding site.] A resin composition comprising a maleimide compound having a partial structure represented by the formula, (B) an active ester compound, and (C) an epoxy resin, wherein the mass ratio of component (A) to component (B) ((content of component (A) / (content of component (B)))) is 1 or more, and the mass ratio of component (A) to component (C) ((content of component (A) / (content of component (C)))) is 0.67 or less.

2. (A) Compound (X1): 【Chemical Formula 2】 [wherein ring X represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; a and b each independently represent 0, 1, 2 or 3, and the sum of a and b is 1 to 5; * represents a bonding site.] A resin composition comprising a maleimide compound having a partial structure represented by the formula, (B) an active ester compound, and (C) an epoxy resin, wherein the mass ratio of component (A) to component (B) ((content of component (A) / (content of component (B)))) is 10 / 11 or more, and the mass ratio of component (A) to component (C) ((content of component (A) / (content of component (C)))) is 0.56 or less.

3. In addition to the partial structure represented by formula (X1), component (A) further has a partial structure represented by formula (Y1): 【Chemical Formula 3】 [wherein ring Y represents a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; c and d each independently represent 0 or an integer of 1 or more, and the sum of c and d is 6 or more; * represents a bonding site.] The resin composition according to claim 1 or 2, wherein component (A) is a maleimide compound having a partial structure represented by the formula.

4. The resin composition according to any one of claims 1 to 3, wherein the number of maleimide groups in one molecule of component (A) is 2.

5. The resin composition according to any one of claims 1 to 4, wherein component (A) is a maleimide-terminated polyimide.

6. Component (A) has the formula (A1): [Chemical Formula 4] [wherein R １ each independently represents a substituent; ring X and ring Y each independently represent a monocycloalkane ring which may have a substituent or a monocycloalkene ring which may have a substituent; Ring Z each independently represents an optionally substituted non-aromatic ring or an optionally substituted aromatic ring; Z １ and Z ２ each independently represents a single bond, an alkylene group, -O-, -CO-, -S-, -SO-, -SO ２ -, -CONH-, -NHCO-, -COO-, or -OCO-; a and b each independently represent 0, 1, 2 or 3, and the sum of a and b is 1 to 5; c and d each independently represent 0 or an integer of 1 or more, and the sum of c and d is 6 or more; e each independently represents 0 or 1; f each independently represents 0 or an integer of 1 or more; g each independently represents 0, 1 or 2; n1 represents an integer of 1 or more; n2 represents 0 or an integer of 1 or more; m1 and m2 are such that one of them represents 1 and the other represents 0. ] The resin composition according to any one of claims 1 to 5, which is a compound represented by the formula.

7. The resin composition according to any one of claims 1 to 6, wherein the content of component (C) is 10% by mass to 50% by mass when the non-volatile components in the resin composition are 100% by mass.

8. The resin composition according to any one of claims 1 to 7, wherein the content of component (A) is 3% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass.

9. The resin composition according to any one of claims 1 to 8, wherein the content of component (B) is 3% by mass to 30% by mass when the non-volatile components in the resin composition are 100% by mass.

10. The resin composition according to any one of claims 1 to 9, wherein the mass ratio of component (A) to component (B) ((content of component (A)) / (content of component (B))) is 3 or less.

11. The resin composition according to any one of claims 1 to 10, wherein the mass ratio of component (A) to component (C) ((content of component (A)) / (content of component (C))) is 0.1 or more.

12. Further comprising (D) an inorganic filler, The resin composition according to any one of claims 1 to 11, wherein the content of component (D) is 40% by mass or more when the non-volatile components in the resin composition are 100% by mass.

13. The resin composition according to any one of claims 1 to 12, wherein the dielectric tangent (Df) of the cured product of the resin composition is 0.005 or less when measured at 5.8 GHz and 23°C.

14. The resin composition according to any one of claims 1 to 13, wherein the relative dielectric constant (Dk) of the cured product of the resin composition is 3.0 or less when measured at 5.8 GHz and 23°C.

15. The resin composition according to any one of claims 1 to 14, wherein the glass transition temperature (Tg) of the cured product of the resin composition is 150°C or higher.

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

17. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 15.

18. A resin sheet having a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 15 provided on the support.

19. A printed wiring board including an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 15.

20. A semiconductor device including the printed wiring board according to claim 19.

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