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. Furthermore, it relates to a cured product, a sheet-like laminated material, a resin sheet, a printed circuit board, and a semiconductor device obtained using the resin composition. [Background technology]

[0002] As a manufacturing technology for printed circuit boards, a build-up method is known in which insulating layers and conductive layers are stacked alternately. In the build-up method, the insulating layer is generally formed by curing a resin composition. In recent years, there has been a demand for further improvement in dielectric properties such as dielectric constant and dielectric loss tangent of the insulating layer, as well as further improvement in copper adhesion. On the other hand, there is also a demand for insulating layers with a high glass transition temperature.

[0003] Various maleimide compounds containing non-aromatic ring skeletons have been known to date (Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-203122 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a resin composition that can produce a cured product with low relative permittivity (Dk) and dielectric loss tangent (Df), a high glass transition temperature (Tg), and excellent copper adhesion. [Means for solving the problem]

[0006] In order to achieve the object of the present invention, the present inventors 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 dielectric constant (Dk) and a low dielectric tangent (Df), a high glass transition temperature (Tg), and excellent copper adhesion can be obtained, and 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 a partial structure represented by the formula (Y1) in addition to the partial structure represented by the formula (X1):

[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 a compound 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 represents 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 above formula. [6] 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% to 30% by mass, when the nonvolatile components in the resin composition are considered to be 100% by mass. [8] The resin composition according to any one of [1] to [7] above, wherein the content of component (B) is 3% to 30% by mass, when the nonvolatile components in the resin composition are considered to be 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) (component (A) / component (B)) is 0.5 to 3.

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

[11] The resin composition according to any 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 nonvolatile components in the resin composition are taken as 100% by mass.

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

[12] above, wherein the dielectric loss tangent (Df) of the cured 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 permittivity (Dk) of the cured 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 resin composition is 150°C or higher.

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

[15] above.

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

[15] above.

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

[15] above, provided on the support.

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

[15] above.

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

[19] above. [Effects of the Invention]

[0014] According to the resin composition of the present invention, a cured product can be obtained that has a low relative permittivity (Dk) and dielectric loss tangent (Df), a high glass transition temperature (Tg), and excellent copper adhesion. [Modes for carrying out the invention]

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

[0016] <Resin composition> The resin composition of the present invention is (A) formula (X1):

[0017] [ka]

[0018] [In the formula, ring X represents an optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring; a and b each independently represent 0, 1, 2, or 3, and the sum of a and b is between 1 and 5; and * indicates a bonding site.] The resin composition contains a maleimide compound having a substructure represented by (B) (which may be referred to as a "specific maleimide compound") and an active ester compound. By using such a resin composition, a cured product can be obtained that has a low dielectric constant (Dk) and dielectric loss tangent (Df), a high glass transition temperature (Tg), and excellent copper adhesion.

[0019] The resin composition of the present invention may further contain any optional components in addition to (A) a specific maleimide compound and (B) an active ester compound. Examples of optional components include (A') other radical polymerizable compounds, (C) epoxy resins, (D) inorganic fillers, (E) curing accelerators, (F) other additives, and (G) organic solvents. Each component contained in the resin composition will be described in detail below.

[0020] <(A) Specific maleimide compounds> The resin composition of the present invention comprises (A) a specific maleimide compound. A maleimide compound means a compound that contains at least one maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group) in one molecule. The number of maleimide groups in one molecule of (A) the specific maleimide compound is preferably two or more, and particularly preferably two. (A) The specific maleimide compound may be used alone, or two or more may be used in any ratio.

[0021] (A) A specific maleimide compound is given by formula (X1):

[0022] [ka]

[0023] [In the formula, ring X represents an optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring; a and b each independently represent 0, 1, 2, or 3, and the sum of a and b is between 1 and 5; and * indicates a bonding site.] It has a substructure represented by [the symbol].

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

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

[0026] In this specification, "substituent" is not particularly limited, but examples include monovalent substituents such as alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups (alkyl groups substituted with aryl groups), alkyl-oxy groups, alkenyl-oxy groups, aryl-oxy groups, alkyl-carbonyl groups, alkenyl-carbonyl groups, aryl-carbonyl groups, alkyl-oxy-carbonyl groups, alkenyl-oxy-carbonyl groups, aryl-oxy-carbonyl groups, alkyl-carbonyl-oxy groups, alkenyl-carbonyl-oxy groups, and aryl-carbonyl-oxy groups. Divalent substituents such as oxo groups (=O) may also be included if they are substituted.

[0027] Alkyl(group) refers to a linear, branched, and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, alkyl(groups) having 1 to 14 carbon atoms are preferred. Examples of alkyl(groups) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, and cyclohexylmethyl. Alkenyl(group) refers to a linear, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, alkenyl(groups) having 2 to 14 carbon atoms are preferred. Examples of alkenyl groups include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and cyclohexenyl groups. An aryl group refers to a monovalent aromatic hydrocarbon group. Unless otherwise specified, aryl groups with 6 to 14 carbon atoms are preferred. Examples of aryl groups include phenyl, 1-naphthyl, and 2-naphthyl groups.

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

[0029] a and b independently represent 0, 1, 2, or 3, and the sum of a and b is between 1 and 5. Preferably, a and b independently represent 0, 1, or 2, and the sum of a and b is 1 or more. More preferably, a and b independently represent 0 or 1, and the sum of a and b is 1 or more. Particularly preferably, one of a and b is 1 and the other is 0.

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

[0031] [ka]

[0032] [In the formula, R 2 Each of these independently represents an alkyl group; x represents an integer from 0 to 5; and other symbols are as described above. This is a substructure represented by [this].

[0033] R 2 Each of these independently represents an alkyl group. 2 Each of these is independently 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, even more preferably 2, 3 or 4, and particularly preferably 3.

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

[0035] [ka]

[0036] [In the formula, * is the same as above.] This is a substructure represented by [this].

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

[0038] (A) The specific maleimide compound preferably has a substructure represented by formula (X1) in addition to formula (Y1):

[0039] [ka]

[0040] [In the formula, ring Y represents an optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring; c and d are independently 0 or an integer of 1 or greater, and the sum of c and d is 6 or greater; * represents a bonding site.] It has a substructure represented by [the symbol].

[0041] Ring Y represents a monocycloalkane ring or a monocycloalkene ring, which may have substituents. Preferably, Ring Y is a monocycloalkane ring or a monocycloalkene ring, which may be substituted with a group selected from alkyl groups and alkenyl groups. More preferably, Ring Y is a monocycloalkane ring with 4 to 10 carbon atoms, which may be substituted with a group selected from alkyl groups with 1 to 14 carbon atoms and alkenyl groups with 1 to 14 carbon atoms, or a monocycloalkene ring with 4 to 10 carbon atoms, which may be substituted with a group selected from alkyl groups with 1 to 14 carbon atoms and alkenyl groups with 1 to 14 carbon atoms. Even more preferably, Ring Y is a monocycloalkane ring with 4 to 10 carbon atoms, which may be substituted with a group selected from alkyl groups with 1 to 14 carbon atoms. Particularly preferably, Ring Y is a cyclohexane ring, which may be substituted with a group selected from alkyl groups with 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.

[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.] This is a substructure represented by [this].

[0050] (A) The number of substructures represented by formula (Y1) in one molecule of a specific maleimide compound is at least 1, preferably 2 or more, and the upper limit may 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-like polyimide (a chain-like polymer containing an imide structure in its repeating units) having maleimide groups at both ends. Maleimide-terminated polyimides are known to be obtained, for example, by imidizing a component containing a diamine compound, maleic anhydride, and tetracarboxylic dianhydride.

[0052] (A) A specific maleimide compound is, in one embodiment, of formula (n1):

[0053] [ka]

[0054] [In the formula, R 1 Each of these independently represents a substituent; each of the rings Z independently represents a non-aromatic ring which may have substituents, or an aromatic ring which may have substituents; Z 1 and Z 2 Each of the following independently represents a single bond, an alkylene group, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-; each of the following independently represents 0 or 1; each of the following independently represents 0 or an integer greater than or equal to 1; each of the following independently represents 0, 1, or 2; and other symbols are as described above. Preferably, the maleimide compound contains a structural unit represented by formula (n1), and further contains a structural unit represented by formula (n2):

[0055] [ka]

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

[0057] R 1 Each of these independently represents a substituent, preferably an alkyl group. Each of the rings Z independently represents a non-aromatic ring which may have substituents, or an aromatic ring which may have substituents, preferably an aromatic ring which may have substituents.

[0058] An aromatic ring is a ring that follows Hückel's rule, where the number of electrons in the π-electron system on the ring is 4p+2 (where p is a natural number). An aromatic ring can be an aromatic carbocyclic ring with carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms, but in one embodiment, an aromatic carbocyclic ring is preferred. In one embodiment, an aromatic ring with 5 to 14 members is preferred, an aromatic ring with 5 to 10 members is more preferred, and an aromatic ring with 5 or 6 members is even more preferred. Suitable specific examples of aromatic rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and the like, more preferably benzene rings or naphthalene rings, and particularly preferably benzene rings.

[0059] A non-aromatic ring refers to a ring other than an aromatic ring. A non-aromatic ring may be a non-aromatic carbocyclic ring with carbon atoms as ring constituent atoms, or a non-aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen, or sulfur atoms in addition to carbon atoms as ring constituent atoms, but in one embodiment, it is preferable to be a non-aromatic carbocyclic ring. A non-aromatic ring may be a saturated ring or an unsaturated non-aromatic ring, but in one embodiment, it is preferable to be a saturated ring. In one embodiment, a non-aromatic ring with 4 to 14 members is preferred. Examples of non-aromatic rings include monocycloalkane rings such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane rings; monocycloalkene rings such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, and cyclohexadiene rings; and aromatic-non-aromatic ring condensation rings such as indan, indene, tetralin, and fluorene rings.

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

[0061] An alkylene group refers to a straight-chain or branched-chain divalent aliphatic saturated hydrocarbon group. Preferably, the alkylene group has 1 to 14 carbon atoms. Examples of alkylene groups include straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; and branched-chain alkylene groups such as ethylidene (-CH(CH3)-), propyridene (-CH(CH2CH3)-), isopropylidene (-C(CH3)2-), ethylmethylmethylene (-C(CH3)(CH2CH3)-), and diethylmethylene (-C(CH2CH3)2-).

[0062] e represents 0 or 1, preferably 0. Each f independently represents 0 or an integer greater than or equal to 1, preferably 0, 1, or 2. Each g independently represents 0, 1, or 2, preferably 0.

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

[0064] Formula (Z) included in the structural unit represented by formulas (n1) and (n2):

[0065] [ka]

[0066] [In the formula, * is the same as above.] Examples of substructures represented by equations (Z-1) to (Z-25) are:

[0067] [ka]

[0068] [In the formula, * is the same as above.] Examples of substructures include those represented by any of the following, and among them, the substructure represented by formula (Z-1) is preferred.

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

[0070] [ka]

[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); m1 and m2 represent either 1 or 0; other symbols are as above.] This is a compound represented by (with a bond between the n1 and n2 units). The order and arrangement of the n1 and n2 units are arbitrary, and include alternating copolymers, block copolymers, random copolymers, etc. The n1 and n2 units may be the same or different for each unit.

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

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

[0074] [ka]

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

[0076] [ka]

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

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

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

[0080] (A) Examples of commercially available specific maleimide compounds 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 nonvolatile 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, even 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 nonvolatile 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, even 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 radical polymerizable compounds> The resin composition of the present invention may further contain a radical polymerizable compound (A') other than component (A) as an optional component. The radical polymerizable compound (A') may be used alone or in any combination of two or more types.

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

[0084] (A') Other radical polymerizable compounds can be any known radical polymerizable compound, and are not particularly limited. Examples include maleimide-based radical polymerizable compounds having two or more maleimide groups other than component (A), vinylphenyl-based radical polymerizable compounds having two or more vinylphenyl groups, and (meth)acrylic-based radical polymerizable compounds having two or more acryloyl groups and / or methacryloyl groups.

[0085] Maleimide-based radical polymerizable compounds are not particularly limited and may be aliphatic maleimide compounds containing an aliphatic amine skeleton or aromatic maleimide compounds containing an aromatic amine skeleton. Examples of commercially available products include "BMI-1500," "BMI-1700," "BMI-3000J," "BMI-689," and "BMI-2500" (maleimide compounds containing a dimer amine structure) from Designer Molecules, "BMI-6100" (aromatic maleimide compound) from Designer Molecules, "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aralkyl type maleimide compounds) from Nippon Kayaku Co., Ltd., "BMI-70" and "BMI-80" from K.I. Chemicals, Inc., and "BMI-2300" and "BMI-TMH" from Yamato Chemical Industries, Ltd. Furthermore, as a maleimide-based radical polymerizable compound, a maleimide resin (indane ring skeleton-containing maleimide compound) disclosed in the Japan Institute of Invention and Innovation Publication No. 2020-500211 may be used.

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

[0087] The (meth)acrylic radical polymerizable compound is not particularly limited, but in one embodiment, it is preferably a thermoplastic resin having acryloyl groups and / or methacryloyl groups, and more preferably a resin selected from modified polyphenylene ether resins having acryloyl groups and / or methacryloyl groups, and modified polystyrene resins having acryloyl groups and / or methacryloyl groups. Examples of commercially available products include "SA9000" and "SA9000-111" (methacrylic modified polyphenylene ether resin) manufactured by SABIC Innovative Plastics.

[0088] (A') The functional group equivalent of the other radical polymerizable compound 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. (A') The functional group equivalent of the other radical polymerizable compound is the mass of the other radical polymerizable compound 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 the other radical polymerizable compounds is preferably 500 to 50,000, more preferably 700 to 20,000. (A') The number-average molecular weight (Mn) of the other radical polymerizable compounds is preferably 500 to 50,000, more preferably 700 to 20,000.

[0090] The content of (A') other radical polymerizable compounds in the resin composition is not particularly limited, but when the nonvolatile components in the resin composition are taken as 100% by mass, it is preferably 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 (A') other radical polymerizable compounds in the resin composition is not particularly limited, but when the nonvolatile components in the resin composition are taken as 100% by mass, it may be, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, etc.

[0091] The content of the (A) specific maleimide compound in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, when the total radical polymerizable compounds in the resin composition (the sum of components (A) and (A')) are taken as 100% by mass.

[0092] <(B) Active ester compounds> The resin composition of the present invention contains (B) an 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 (C) an epoxy resin, or when the resin composition is mixed with (C) an epoxy resin, the (B) active ester compound may function as an epoxy resin curing agent that reacts with the (C) epoxy resin to cure it.

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

[0094] Specifically, (B) the active ester compound is preferably a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, or an active ester compound containing a benzoylated phenol novolac. More preferably, it is at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds, with dicyclopentadiene-type active ester compounds being even more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

[0095] (B) Commercially available active ester compounds include, as active ester compounds containing a dicyclopentadiene-type diphenol structure, "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 active ester compounds containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", Examples include "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", and "EXB-8" (manufactured by DIC Corporation); as a phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC Corporation); as an active ester compound that is an acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester compound that is a benzoylated phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and as an active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Corporation).

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

[0097] The content of the (B) active ester compound in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are taken as 100% by mass, it is preferably 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 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, but 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, even 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 specific maleimide compound (A) to the active ester compound (B) in the resin composition (component (A) / component (B)) is preferably 0.1 or higher, more preferably 0.5 or higher, and particularly preferably 0.7 or higher. The upper limit of the mass ratio of the specific maleimide compound (A) to the active ester compound (B) in the resin composition (component (A) / component (B)) is preferably 10 or lower, more preferably 3 or lower, and particularly preferably 1.5 or lower.

[0099] <(C) Epoxy resin> The resin composition of the present invention may optionally contain (C) epoxy resin. (C) epoxy resin is a curable resin having epoxy groups.

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

[0101] The resin composition preferably contains an epoxy resin having two or more epoxy groups per molecule as (C) epoxy resin. The proportion of epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the nonvolatile component of (C) epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0102] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only liquid epoxy resin, or only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin, or a combination of liquid epoxy resin and 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] Preferred liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine 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.

[0105] Specific examples of liquid epoxy resins include DIC's "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US," "828EL," "jER828EL," "825," and "Epicote 828EL" (bisphenol A-type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F-type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac-type epoxy resin); Mitsubishi Chemical's "630," "630LSD," and "604" (glycidylamine-type epoxy resin); ADEKA's "ED-523T" (glycyrrhizol-type epoxy resin); ADEKA's "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resin) Examples include lysidylamine-type epoxy resins; "EP-4088S" (dicyclopentadiene-type epoxy resin) from ADEKA Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) from Nippon Steel Chemical & Material Chemicals Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) from Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) from Daicel Corporation; "PB-3600" from Daicel Corporation, "JP-100" and "JP-200" (epoxy resins with a butadiene structure) from Nippon Soda Co., Ltd.; and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) from Nippon Steel Chemical & Material Chemicals Co., Ltd. These can be used individually or in combination of two or more types.

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

[0107] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolac-type epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, phenol aralkyl-type epoxy resin, tetraphenylethane-type epoxy resin, phenolphthalein-type epoxy resin, and phenolphthalein-type epoxy resin.

[0108] Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" (cresol novolac-type epoxy resin); DIC's "N-695" (cresol novolac-type epoxy resin); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resins); and DIC's "EXA-7311". "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V", "ESN4 100V (naphthalene-type epoxy resin); "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "Y Examples include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) from Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) from Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) from Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) from Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalein type epoxy resin) from Nippon Kayaku Co., Ltd.These may be used individually or in combination of two or more types.

[0109] (C) When using both liquid epoxy resin and solid epoxy resin as the epoxy resin, the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin / solid epoxy resin) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, even 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., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[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 even more preferably 400 to 1,500. The weight-average molecular weight of the resin can be measured as a polystyrene equivalent by gel permeation chromatography (GPC).

[0112] The content of (C) epoxy resin in the resin composition is not particularly limited, but when the nonvolatile components in the resin composition are taken as 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, even 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 (C) epoxy resin in the resin composition is not particularly limited, but when the nonvolatile components in the resin composition are taken as 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, even 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 (component (A) / component (C)) is preferably 0.1 or higher, more preferably 0.3 or higher, and particularly preferably 0.5 or higher. The upper limit of the mass ratio of the (A) specific maleimide compound to the (C) epoxy resin in the resin composition (component (A) / component (C)) 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 (D) an inorganic filler as an optional component. (D) The inorganic filler is included in the resin composition in the form of particles.

[0115] (D) Inorganic compounds are used as the material for the inorganic filler. (D) Examples of materials for the 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 tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred as the silica. (D) The inorganic filler may be used alone or in combination of two or more types in any ratio.

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

[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, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. (D) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (D) The average particle size of the inorganic filler can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the median diameter can be used as the average particle size. A sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them with ultrasound for 10 minutes. The particle size distribution of the inorganic filler was measured using a laser diffraction particle size distribution analyzer with blue and red light source wavelengths, employing a flow cell method. The average particle size was calculated as the median diameter from the obtained particle size distribution. Examples of laser diffraction particle size distribution analyzers include the "LA-960" manufactured by Horiba, Ltd.

[0118] (D) The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m². 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 (D) The upper limit of the specific surface area of ​​the inorganic filler is not particularly limited, but preferably 100 m². 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2 The value is less than / g. The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0119] (D) The inorganic filler is preferably surface-treated with an appropriate surface treatment agent. Surface treatment can improve the moisture resistance and dispersibility of the inorganic filler (D). Examples of surface treatment agents 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; and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and N-2-(aminoethyl)-3-aminopropyl Amino-based silane coupling agents such as dimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, 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, 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatetopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; and other silane coupling agents.Examples include alkylalkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane. Furthermore, the surface treatment agent may be used alone or in combination of two or more agents in any ratio.

[0120] Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd.'s "KBM-1003", "KBE-1003" (vinyl silane coupling agent); "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styryl silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino silane coupling agent). Examples of coupling agents include: "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802" and "KBM-803" (mercapto-based silane coupling agents); "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", and "KBM-7103" (alkylalkoxysilane compounds).

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

[0122] The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler should be 0.02 mg / m². 2 The above is preferred, and 0.1 mg / m² 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in sheet form, 1.0 mg / m² 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2 The following are even more preferable.

[0123] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after cleaning the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) after surface treatment. Specifically, a sufficient amount of MEK as the solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, a Horiba "EMIA-320V" or similar can be used.

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

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

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

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

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

[0129] Examples of urea-based curing accelerators include aliphatic dimethylureas such as 1,1-dimethylurea, 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. Aromatic dimethylureas such as toluenebisdimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] are examples.

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

[0131] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-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 isocyanurate adduct, 2-phenylimidazole isocyanurate adduct Examples include imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins.

[0132] Commercially available imidazole-based curing accelerators may be used, such as "1B2PZ," "2MZA-PW," and "2PHZ-PW" from Shikoku Chemicals, and "P200-H50" from Mitsubishi Chemical Corporation.

[0133] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include 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 organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0134] Examples of amine-based curing accelerators 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 an amine-based curing accelerator, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd.

[0136] The content of (E) curing accelerator in the resin composition is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass. The lower limit of the content of (E) curing accelerator in the resin composition is not particularly limited, but is, 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, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0137] <(F) Other additives> The resin composition of the present invention may further contain any additives as non-volatile components. Such additives include, for example, 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 phenol-based 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, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins; organic fillers such as rubber particles; organometallic compounds such as organocenium compounds, organozinc compounds, and organocalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; and vent Thickeners such as montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion improvers such as triazole-based adhesion improvers, tetrazole-based adhesion improvers, and triazine-based adhesion improvers; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (e.g., phosphate ester compounds) Examples of flame retardants include 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 dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers.(F) Other additives may be used individually or in combination of two or more in any ratio. (F) The content of other additives can be appropriately determined by a person skilled in the art.

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

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

[0140] <Method for producing resin compositions> 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 radical 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, in any order and / or partially or entirely simultaneously, and mixing them in any preparation container. The temperature can be set appropriately during the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout the process. The resin composition may also be stirred or shaken using, for example, a stirring device such as a mixer or a shaking device to disperse it uniformly during or after the process of adding and mixing. Degassing may also be performed simultaneously with stirring or shaking under low-pressure conditions such as vacuum.

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

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

[0143] The cured product of the resin composition of the present invention may have the characteristic of having a low dielectric constant (Dk). Therefore, in one embodiment, the dielectric constant (Dk) of the cured product of the resin composition measured at 5.8 GHz and 23°C as in Test Example 1 below may be preferably 5.0 or less, more preferably 4.0 or less, even 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 the characteristic of having a high glass transition temperature (Tg). Therefore, in one embodiment, the glass transition temperature (Tg) measured as in Test Example 2 below may be preferably 120°C or higher, more preferably 140°C or higher, even 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 the characteristic of excellent copper adhesion. Therefore, in one embodiment, the adhesion strength to the underlying copper (copper foil) measured in accordance with JIS C6481 as shown in Test Example 5 below may be preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, even more preferably 0.4 kgf / cm or more, and particularly preferably 0.5 kgf / cm or more. There is no particular upper limit, but for example it may be 10 kgf / cm or less. Also, in one embodiment, a copper-plated conductor layer is formed on the cured product as shown in Test Example 4 below, and the copper plating peel strength calculated from the load when the copper-plated conductor layer is peeled off in the vertical direction may be preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, even more preferably 0.35 kgf / cm or more, and particularly preferably 0.4 kgf / cm or more. There is no particular upper limit, but for example it may be 10 kgf / cm or less.

[0146] In one embodiment, the cured product of the resin composition of the present invention may have the characteristic of having a low arithmetic mean roughness (Ra) of the surface after roughening treatment. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the surface of the cured product after roughening treatment, as measured as in Test Example 3 below, may be preferably 300 nm or less, more preferably 200 nm or less, even 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 may be, for example, 1 nm or more, 2 nm or more, etc.

[0147] <Uses of resin compositions> The resin composition of the present invention can be suitably used as a resin composition for insulating applications, particularly as a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (including a redistribution layer) on which a conductor layer (including a redistribution layer) is formed (a resin composition for forming an insulating layer for forming a conductor layer). Furthermore, in printed circuit boards described later, it can be suitably used as a resin composition for forming an insulating layer on a printed circuit board (a resin composition for forming an insulating layer on a printed circuit board). The resin composition of the present invention can also be used in a wide range of applications where a resin composition is required, such as sheet-like laminated materials like resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins.

[0148] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a redistribution-forming layer (resin composition for forming a redistribution-forming layer) as an insulating layer for forming a redistribution layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When the semiconductor chip package is manufactured, a redistribution layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto the substrate, (2) A step of temporarily fixing the semiconductor chip onto a temporary fixing film, (3) A step of forming a sealing layer on a semiconductor chip, (4) Steps to peel off the substrate and temporary fixing film from the semiconductor chip, (5) A step of forming a rewiring layer as an insulating layer on the surface from which the substrate and temporary fixing film of the semiconductor chip have been peeled off, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer.

[0149] Furthermore, since the resin composition of the present invention provides an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a circuit board with embedded components.

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

[0151] As sheet-like laminated materials, the following resin sheets and prepregs are preferred.

[0152] In one embodiment, the resin sheet comprises a support and a resin composition layer provided on the support, the resin composition layer being formed from the resin composition of the present invention.

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

[0154] Examples of support materials include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

[0155] When using a film made of plastic material as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

[0157] The support may have a matte finish, corona treatment, or antistatic treatment applied to the surface that bonds with the resin composition layer.

[0158] Furthermore, as the support, a support with a release layer may be used, which has a release layer on the surface that is bonded to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may be used as the support with a release layer, for example, PET films having a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1", "AL-5", and "AL-7" from Lintec Corporation, "Lumirror T60" from Toray Industries, Inc., "Purex" from Teijin Corporation, and "Unipeel" from Unitika Corporation.

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

[0160] In one embodiment, the resin sheet may further include any additional layer as needed. Such an additional layer may be, for example, a protective film similar to the support, provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of dust and other debris to the surface of the resin composition layer and scratches can be suppressed.

[0161] Resin sheets can be manufactured, for example, by applying a resin varnish prepared by directly using a liquid resin composition or by dissolving the resin composition in an organic solvent, coating it onto a support using a die coater or the like, and then drying it to form a resin composition layer.

[0162] Examples of organic solvents include those similar to those described as components of the resin composition. Organic solvents may be used individually or in combination of two or more.

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

[0164] The resin sheet can be stored by rolling it up. If the resin sheet has a protective film, it can be used after removing the protective film.

[0165] In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous substrate with the resin composition of the present invention.

[0166] The sheet-like fibrous substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed circuit board, the thickness of the sheet-like fibrous substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous substrate is not particularly limited, but is usually 10 μm or more.

[0167] Prepregs can be manufactured by known methods such as the hot melt method and the solvent method.

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

[0169] The sheet-like laminated material of the present invention can be suitably used to form an insulating layer of a printed circuit board (for the insulating layer of a printed circuit board), and more suitably used to form an interlayer insulating layer of a printed circuit board (for the interlayer insulating layer of a printed circuit board).

[0170] <Printed wiring board> The printed circuit board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

[0171] Printed circuit boards can be manufactured, for example, using the resin sheet described above, by a method including the following steps (I) and (II). (I) A process of laminating a resin sheet onto an inner layer substrate such that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., thermal curing) the resin composition layer to form an insulating layer.

[0172] The "internal layer substrate" used in process (I) is a material that serves as the substrate for a printed wiring board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. The substrate may also have a conductive layer on one or both sides, and this conductive layer may be patterned. An internal layer substrate in which a conductive layer (circuit) is formed on one or both sides of the substrate is sometimes called an "internal layer circuit board." Furthermore, an intermediate product on which an insulating layer and / or a conductive layer is to be formed during the manufacturing of a printed wiring board is also included in the "internal layer substrate" as defined in this invention. If the printed wiring board is a circuit board with embedded components, an internal layer substrate with embedded components may be used.

[0173] Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet onto the inner layer substrate from the support side. Examples of the member used to heat and press the resin sheet onto the inner layer substrate (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS end plate) or a metal roll (such as a SUS roll). It is preferable to press the resin sheet via an elastic material such as heat-resistant rubber, rather than directly pressing the heat-pressing member onto the resin sheet, so that the resin sheet can adequately follow the surface irregularities of the inner layer substrate.

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

[0175] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch-type vacuum pressure laminators.

[0176] After lamination, the laminated resin sheets may be smoothed by pressing a heat-sealing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for lamination. The smoothing process can be performed using a commercially available laminator. Lamination and smoothing may be performed continuously using the commercially available vacuum laminator mentioned above.

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

[0178] In step (II), the resin composition layer is cured (e.g., by thermal curing) to form an insulating layer made of the cured resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions commonly used when forming an insulating layer for a printed circuit board may be used.

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

[0180] Prior to thermal curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermal curing the resin composition layer, it may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0181] In manufacturing printed circuit boards, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer. These steps (III) through (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed circuit boards. If the support is removed after step (II), the removal of the support may be carried out between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (II) through (V) may be repeated to form a multilayer circuit board.

[0182] In other embodiments, the printed circuit board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as when a resin sheet is used.

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

[0184] Step (IV) is a process for roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The procedure and conditions for the roughening process are not particularly limited, and known procedures and conditions commonly used when forming the insulating layer of a printed circuit board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution in this order.

[0185] The swelling solution used for the roughening treatment is not particularly limited, but examples include alkaline solutions and surfactant solutions, and is preferably an alkaline solution, with sodium hydroxide solution and potassium hydroxide solution being more preferred. Examples of commercially available swelling solutions include "Swelling Dip Securing P" and "Swelling Dip Securing SBU" manufactured by Atotec Japan. The swelling treatment with the swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0186] The oxidizing agent used for the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Attec Japan.

[0187] Furthermore, an acidic aqueous solution is preferred as the neutralizing solution used in the roughening treatment. A commercially available example is "Reduction Solution Securigant P" manufactured by Attec Japan.

[0188] The neutralization treatment can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in a neutralization solution at 30°C to 80°C for 5 to 30 minutes. From the standpoint of workability, it is preferable to immerse the object, which has been roughened with an oxidizing agent, in a neutralization solution at 40°C to 70°C for 5 to 20 minutes.

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

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

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

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

[0193] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using conventionally known techniques such as the semi-additive method or the fully additive method. From the viewpoint of ease of manufacture, it is preferable to form it by the semi-additive method. An example of forming the conductor layer by the semi-additive method is shown below.

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

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

[0196] Metal foils can be manufactured by known methods such as electrolysis and rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Oil & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0197] <Semiconductor device> The semiconductor device of the present invention includes the printed circuit board of the present invention. The semiconductor device of the present invention can be manufactured using the printed circuit board of the present invention.

[0198] Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Examples]

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

[0200] <Example 1> 20 parts of an isophorone diamine skeleton-containing maleimide compound (SLK-2600, manufactured by Shin-Etsu Chemical Co., Ltd., 50% solids by mass anisole solution, main component (non-volatile component): maleimide compound represented by the following formula (A)), 17.7 parts of an active ester compound (HPC-8150-62T, manufactured by DIC Corporation, 62% solids by mass toluene solution), 18 parts of naphthol aralkyl epoxy resin (ESN-475V, manufactured by Nippon Steel Chemical & Material Co., Ltd.), and spherical silica surface-treated with a silane coupling agent (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) (SO-C2, manufactured by Admatex Corporation, average particle size 0.5 μm, specific surface area 5.8 m²). 2 60 parts of (1 / g), 1 part of an imidazole-based curing accelerator (Shikoku Chemicals Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole), and 20 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin composition (resin varnish).

[0201] [ka]

[0202] <Example 2> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of active ester compound (DIC Corporation's "HPC-8150-62T", a toluene solution with a solid content of 62% by mass) used was changed from 17.7 parts to 16.1 parts, the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical & Material Co., Ltd.'s "ESN-475V") used was changed from 18 parts to 15 parts, and an additional 5.7 parts of biphenyl aralkyl novolac type polymaleimide (Nippon Kayaku Co., Ltd.'s "MIR-3000-70MT", a MEK / toluene mixed solution with a solid content of 70%) was used.

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

[0204] [ka]

[0205] A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of active ester compound (DIC Corporation's "HPC-8150-62T", a toluene solution with a solid content of 62% by mass) used was changed from 17.7 parts to 16.1 parts, the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical & Material Corporation's "ESN-475V") used was changed from 18 parts to 15 parts, and an additional 5.7 parts of maleimide compound A (a MEK solution with a solid content of 70%) was used.

[0206] <Example 4> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of active ester compound (DIC Corporation's "HPC-8150-62T", a toluene solution with a solid content of 62% by mass) used was changed from 17.7 parts to 16.1 parts, the amount of naphthol aralkyl epoxy resin (Nippon Steel Chemical & Material Co., Ltd.'s "ESN-475V") used was changed from 18 parts to 15 parts, and an additional 6.2 parts of terminally vinyl benzylated PPE compound (Mitsubishi Gas Chemical Co., Ltd.'s "OPE-2St 1200", a toluene mixed solution with a solid content of 65%) was used.

[0207] <Example 5> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of active ester compound (DIC Corporation's "HPC-8150-62T", a toluene solution with a solid content of 62% by mass) used was changed from 17.7 parts to 16.1 parts, the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical & Material Corporation's "ESN-475V") used was changed from 18 parts to 15 parts, and an additional 6.2 parts of divinylbenzene / styrene copolymer (Nippon Steel Chemical & Material Corporation's "ODV-XET-X04", a toluene solution with a solid content of 65%) was used.

[0208] <Example 6> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that the amount of active ester compound (DIC Corporation's "HPC-8150-62T", a toluene solution with a solid content of 62% by mass) used was changed from 17.7 parts to 16.1 parts, the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical & Material Corporation's "ESN-475V") used was changed from 18 parts to 15 parts, and an additional 8 parts of terminal methacrylic modified PPE compound (Sabic Innovative Plastics Corporation's "SA9000-111", adjusted to a 50% solid content solution with toluene) were used.

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

[0210] <Comparative Example 2> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 14.3 parts of biphenylaralkyl novolac type polymaleimide (MIR-3000-70MT, manufactured by Nippon Kayaku Co., Ltd., a MEK / toluene mixed solution with 70% solids content) were used instead of 20 parts of an isophoronediamine skeleton-containing maleimide compound (SLK-2600, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0211] <Comparative Example 3> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 20 parts of an isophorone diamine skeleton-containing maleimide compound (SLK-2600, manufactured by Shin-Etsu Chemical Co., Ltd.) were not used, 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 naphthol aralkyl type epoxy resin (ESN-475V, manufactured by Nippon Steel Chemical & Material Co., Ltd.) was changed from 18 parts to 23 parts.

[0212] <Comparative Example 4> A resin composition (resin varnish) was prepared in the same manner as in Example 1, except that 17.7 parts of the active ester compound (DIC Corporation's "HPC-8150-62T", a toluene solution with a solid content of 62% by mass) was not used, the amount of spherical silica (Admatex Corporation's "SO-C2") surface-treated with a silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-573") was changed from 60 parts to 51 parts, and an additional 8.3 parts of a phenolic epoxy curing agent (DIC Corporation's "LA-7054", a MEK solution with a solid content of 60%) was used.

[0213] <Test Example 1: Measurement of Relative Permittivity (Dk) and Dielectric Loss Tangent (Df)> A polyethylene terephthalate film (AL5, manufactured by Lintec Corporation, 38 μm thick) with a release layer was prepared as a support. The resin compositions obtained in the examples and comparative examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. The resin composition was then dried at 80°C to 100°C (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 the support from resin sheet A after removing it from the oven, a cured resin composition layer was obtained. This cured material was cut into pieces 80 mm long and 2 mm wide and designated as cured material B for evaluation.

[0215] For evaluation cured material B, the dielectric constant (Dk value) and dielectric loss tangent (Df value) were measured using the cavity resonance perturbation method with an Agilent Technologies HP8362B at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on two test specimens, 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 then peeled off the support to obtain a cured film. This cured film was cut into pieces 20 mm long and 6 mm wide to serve as evaluation samples. The glass transition temperature (Tg) of these evaluation samples was measured using a Rigaku TMA (thermomechanical analyzer) at a heating rate of 5°C / min from 25°C to 250°C. Two measurements were performed on the same test piece, and the second value was recorded.

[0217] <Test Example 3: Measurement of Arithmetic Mean Roughness (Ra)> (1) Preparation of the inner layer substrate A glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with an inner layer circuit was subjected to a 1 μm roughening treatment of the copper surface by etching both sides with a micro-etching agent (MEC "CZ8101").

[0218] (2) Lamination of resin sheet A Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"), resin sheet A obtained in Test Example 1 was laminated to both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. Lamination was performed by reducing the pressure to 13 hPa or less by depressurizing for 30 seconds, and then pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Subsequently, a hot press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0219] (3) Thermocuring of the resin composition layer Subsequently, the inner layer substrate laminated with resin sheet A was placed in a 130°C oven and heated for 30 minutes, then transferred to a 170°C oven and heated for another 30 minutes to heat-cur the resin composition layer and form an insulating layer. After that, the support was peeled off to obtain a cured substrate A having the insulating layer, inner layer substrate, and insulating layer in that order.

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

[0221] (Wet desmear treatment) The cured substrate A was immersed in a swelling solution (Atotec Japan's "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 (Atotec Japan's "Concentrate Compact CP," an aqueous solution of potassium permanganate at approximately 6% and sodium hydroxide at approximately 4%) at 80°C for 20 minutes. Next, it was immersed in a neutralizing solution (Atotec Japan's "Reduction Solution Securigant P," an aqueous sulfuric acid solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

[0222] (5) Measurement of the arithmetic mean roughness (Ra) of the insulating layer surface after 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 the VSI mode with a 50x lens and a measurement range of 121 μm × 92 μm. 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 patterned 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 performed 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. Further, 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. On these resin composition layers, the treated surface of the CZ copper foil of "3EC-III" was laminated under the same conditions as the lamination of Resin Sheet A in Test Example 1. Then, a sample was produced by curing the resin composition layer under the curing conditions of 190°C for 90 minutes to form an insulating layer.

[0227] (3) Measurement of Copper Foil Peel Strength (Adhesion to Substrate) The produced sample was cut into small pieces of 150×30 mm. Using a cutter, a cut was made in a 10-mm-wide and 100-mm-long portion of the copper foil part of the small piece, 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 amounts of non-volatile components used in the resin compositions of 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, Comparative Examples 2 and 3, which do not use (A) the specific maleimide compound, exhibit low copper foil adhesion and high dielectric constant (Dk) and dielectric loss tangent (Df). Furthermore, Comparative Example 1, which uses a maleimide compound consisting of a dimer amine skeleton instead of (A) the specific maleimide compound, exhibits a low glass transition temperature (Tg). Comparative Example 4, which uses a phenolic curing agent instead of (B) the active ester compound as the epoxy curing agent, exhibits very high dielectric constant (Dk) and dielectric loss tangent (Df). In contrast, it can be seen that these problems can be overcome when using the resin composition of the present invention containing (A) the specific maleimide compound and (B) the active ester compound.

Claims

1. (A) Equation (X1): 【Chemistry 1】 [In the formula, Ring X represents a optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring; a and b independently represent 0, 1, 2, or 3, and the sum of a and b is between 1 and 5; * indicates the binding site. A resin composition comprising (B) a maleimide compound having a substructure represented by (C), an active ester compound, and an epoxy resin, The mass ratio of component (A) to component (B) (content of component (A) / content of component (B)) is 1 or greater. A resin composition in which the mass ratio of component (A) to component (C) (content of component (A) / content of component (C)) is 0.67 or less.

2. (A) Equation (X1): 【Chemistry 2】 [In the formula, Ring X represents a optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring; a and b independently represent 0, 1, 2, or 3, and the sum of a and b is between 1 and 5; * indicates the binding site. A resin composition comprising (B) a maleimide compound having a substructure represented by (C), an active ester compound, and an epoxy resin, The mass ratio of component (A) to component (B) (content of component (A) / content of component (B)) is 10 / 11 or greater. A resin composition in which the mass ratio of component (A) to component (C) (content of component (A) / content of component (C)) is 0.56 or less.

3. (A) In addition to the substructure represented by formula (X1), component (Y1) is further: 【Transformation 3】 [In the formula, Ring Y represents a optionally substituted monocycloalkane ring or an optionally substituted monocycloalkene ring; c and d each independently represent an integer of 0 or greater than or equal to 1, and the sum of c and d is 6 or greater; * indicates the binding site. The resin composition according to claim 1 or 2, which is a maleimide compound having a substructure represented by .

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

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

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

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 nonvolatile components in the resin composition are considered to be 100% by mass.

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

9. The resin composition according to any one of claims 1 to 8, wherein the content of component (B) is 3% to 30% by mass, when the nonvolatile components in the resin composition are considered to be 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. Furthermore, (D) containing 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 nonvolatile components in the resin composition are taken as 100% by mass.

13. The resin composition according to any one of claims 1 to 12, wherein the dielectric loss tangent (Df) of the cured 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 permittivity (Dk) of the cured 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 described in any one of claims 1 to 15, provided on the support.

19. A printed circuit board comprising an insulating layer made of a cured resin composition according to any one of claims 1 to 15.

20. A semiconductor device comprising a printed circuit board as described in claim 19.

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