JP7409223B2 - resin composition - Google Patents

Description

The present invention relates to a resin composition containing a maleimide compound. Furthermore, the present invention relates to a cured product, a sheet-like laminate material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

As a manufacturing technique for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductive layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition. In recent years, there has been a demand for further improvements in dielectric properties such as dielectric constant and dielectric loss tangent of insulating layers, and further improvements in copper adhesion. In addition, an insulating layer with a high glass transition temperature is required.

Until now, maleimide compounds containing various non-aromatic ring skeletons have been known (Patent Document 1).

JP2019-203122A

An object of the present invention is to provide a resin composition that has a low dielectric constant (Dk) and a dielectric loss tangent (Df), a high glass transition point (Tg), and can yield a cured product with excellent copper adhesion. There is a particular thing.

In order to achieve the objects of the present invention, the present inventors have made extensive studies and found that (A) a maleimide compound containing a cross-linked ring skeleton and (B) an active ester compound are used as components of the resin composition. It was unexpectedly discovered that a cured product with low dielectric constant (Dk) and dielectric loss tangent (Df), high glass transition point (Tg), and excellent copper adhesion can be obtained, and the present invention has been developed. I ended up completing it.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) a maleimide compound containing a cross-linked ring skeleton, and (B) an active ester compound.
[2] The resin composition according to [1] above, wherein the bridged ring in component (A) is a tricyclic bridged ring.
[3] The resin composition according to [2] above, wherein the tricyclic bridge ring is a tricyclo[5.2.1.0 ^2,6 ]decane ring.
[4] The resin composition according to any one of [1] to [3] above, wherein the number of maleimide groups in one molecule of component (A) is 2.
[5] The resin composition according to any one of [1] to [4] above, wherein component (A) is a maleimide-terminated polyimide containing a crosslinked ring skeleton.
[6] The resin composition according to any one of [1] to [5] above, wherein component (A) further contains an aromatic tetracarboxylic acid diimide skeleton.
[7] The resin composition according to any one of [1] to [6] above, wherein component (A) further contains a monocyclic non-aromatic ring skeleton.
[8] Component (A) is represented by formula (A1):

[In the formula, R ¹ each independently represents a substituent; X and Y ²² each independently represent a single bond or a linking group; Y ¹ and Y ²¹ each independently represent a single bond; represents a bond, an alkylene group, or an alkenylene group; Z and ^Z2 each independently represent a monocyclic non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent. ; Z ¹ each independently represents a bridged ring which may have a substituent; a each independently represents an integer of 0 to 2; b each independently represents , 0 or 1; c, d and n2 each independently represent 0 or an integer of 1 or more; n1 represents an integer of 1 or more; m1 and m2, one of which represents 1; And the other one shows 0. ]
The resin composition according to any one of [1] to [7] above, which is a bismaleimide compound represented by:
[9] The resin composition according to any one of [1] to [8] above, wherein component (A) has a weight average molecular weight of 2,000 to 50,000.
[10] Any one of the above [1] to [9], wherein the content of component (A) is 3% by mass to 30% by mass when the nonvolatile components in the resin composition are 100% by mass. resin composition.
[11] The resin composition according to any one of [1] to [10] above, further comprising (A') a radically polymerizable compound other than component (A).
[12] According to any one of [1] to [11] above, the content of component (A) is 50% by mass or more when the total radically polymerizable compound in the resin composition is 100% by mass. resin composition.
[13] According to any one of [1] to [12] above, the content of component (B) is 3% by mass to 30% by mass when the nonvolatile components in the resin composition are 100% by mass. resin composition.
[14] The mass ratio of component (A) to component (B) (component (A)/component (B)) is 0.5 to 3, according to any one of [1] to [13] above. Resin composition.
[15] The resin composition according to any one of [1] to [14] above, further comprising (C) an epoxy resin.
[16] The resin composition according to any one of [1] to [15] above, further comprising (D) an inorganic filler.
[17] A cured product of the resin composition according to any one of [1] to [16] above.
[18] A sheet-like laminate material containing the resin composition according to any one of [1] to [16] above.
[19] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [16] above, provided on the support.
[20] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [16] above.
[21] A semiconductor device comprising the printed wiring board according to [20] above.

According to the resin composition of the present invention, it is possible to obtain a cured product having a low dielectric constant (Dk) and a dielectric loss tangent (Df), a high glass transition point (Tg), and excellent copper adhesion.

Hereinafter, the present invention will be explained in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof.

<Resin composition>
The resin composition of the present invention includes (A) a maleimide compound containing a cross-linked ring skeleton, and (B) an active ester compound. By using such a resin composition, it is possible to obtain a cured product that has a low dielectric constant (Dk) and a dielectric loss tangent (Df), a high glass transition point (Tg), and excellent copper adhesion.

The resin composition of the present invention may further contain arbitrary components in addition to (A) a maleimide compound containing a cross-linked ring skeleton and (B) an active ester compound. Examples of optional components include (A') other radically polymerizable compounds, (C) epoxy resins, (D) inorganic fillers, (E) curing accelerators, (F) other additives, and (G ) Organic solvents can be mentioned. Each component contained in the resin composition will be explained in detail below.

<(A) Maleimide compound containing a cross-linked ring skeleton>
The resin composition of the present invention includes (A) a maleimide compound containing a crosslinked ring skeleton. (A) A maleimide compound containing a cross-linked ring skeleton refers to a maleimide compound containing at least one cross-linked ring skeleton and at least one maleimide group (2,5-dihydro-2,5-dioxo-1H- It is an organic compound containing a pyrrol-1-yl group). (A) Maleimide compounds containing a bridged ring skeleton may be used alone or in combination of two or more in any ratio.

A bridged ring refers to a bicyclic or more ring system (preferably a bicyclic to hexacyclic ring, particularly preferably a bicyclic to hexacyclic ring) containing two or more non-aromatic rings that share two or more (preferably three or more) atoms. means a non-aromatic ring (tricyclic system). The bridged ring may be a carbocycle having carbon atoms as ring constituent atoms, or a heterocycle having a heteroatom selected from oxygen atoms, nitrogen atoms, and sulfur atoms as ring constituent atoms in addition to carbon atoms. In terms of morphology, it is preferably a carbocyclic ring. In one embodiment, the number of ring atoms in the bridged ring is preferably 6 to 15, more preferably 8 to 12, still more preferably 9 to 11, and particularly preferably 10. The bridged ring may be a saturated ring or an unsaturated ring, but in one embodiment it is preferably a saturated ring. The bridged ring may be substituted with a substituent at a substitutable position.

The bridged ring is not particularly limited, but includes, for example, bicyclo[2.2.1]heptane ring (i.e., norbornane ring), bicyclo[4.4.0]decane ring (i.e., decalin ring) skeleton, bicyclo [5.3.0]decane ring, bicyclo[4.3.0]nonane ring (i.e. hydrindane ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[ 3.3.0]octane ring, bicyclo[3.3.1]nonane ring; tricyclo[5.2.1.0 ^2,6 ]decane ring (i.e., tetrahydrodicyclopentadiene ring); tricyclic bridged rings such as tricyclo[3.3.1.1 ^3,7 ]decane ring (i.e. adamantane ring), tricyclo[6.2.1.0 ^2,7 ]undecane ring, etc. Can be mentioned. In one embodiment, the bridged ring is preferably a tricyclic bridged ring, particularly preferably a tricyclo[5.2.1.0 ^2,6 ]decane ring.

In this specification, the "substituent" is not particularly limited, but includes, for example, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy Examples include monovalent substituents such as a group, aryl-carbonyl-oxy group, etc., and divalent substituents such as an oxo group (=O) may also be included if substitution is possible.

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

(A) The number of cross-linked ring skeletons in one molecule of the maleimide compound containing a cross-linked ring skeleton is preferably 2 or more, and the upper limit may be, for example, 20 or less, 10 or less. (A) The number of maleimide groups in one molecule of the maleimide compound containing a bridged ring skeleton is preferably two or more, and particularly preferably two.

In one embodiment, (A) the maleimide compound containing a bridged ring skeleton preferably further contains a monocyclic non-aromatic ring skeleton in the molecule. The monocyclic non-aromatic ring can be a carbocycle or a heterocycle, but in one embodiment is preferably a carbocycle. In one embodiment, the number of ring atoms of the monocyclic non-aromatic ring is preferably 3 to 10, more preferably 4 to 8, still more preferably 5 or 6, and particularly preferably 6. be. The monocyclic non-aromatic ring may be a saturated ring or an unsaturated ring, but in one embodiment, it is preferably a saturated ring. The monocyclic non-aromatic ring may be substituted with a substituent at a substitutable position.

Examples of monocyclic non-aromatic rings include monocycloalkane rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring; such as cyclopentene ring, cyclohexene ring, and cycloheptene ring. Monocycloalkene ring; monocyclic non-aromatic heterocycles such as a pyrrolidine ring, a tetrahydrofuran ring, a dioxane ring, a tetrahydropyran ring, and the like. In one embodiment, the monocyclic non-aromatic ring is preferably a monocycloalkane ring, particularly preferably a cyclohexane ring.

(A) The number of monocyclic non-aromatic ring skeletons in one molecule of the maleimide compound containing a cross-linked ring skeleton is preferably 2 or more, and the upper limit may be, for example, 20 or less, 10 or less, etc. .

In one embodiment, (A) the maleimide compound containing a cross-linked ring skeleton preferably further contains an aromatic tetracarboxylic acid diimide skeleton in the molecule. Aromatic tetracarboxylic acid diimide is a diimidized structure of aromatic tetracarboxylic acid (eg, benzenetetracarboxylic acid, naphthalenetetracarboxylic acid, anthracenetetracarboxylic acid, diphthalic acid, etc.).

The aromatic tetracarboxylic acid diimide skeleton has the formula (X'):

[In the formula, R ¹ each independently represents a substituent (preferably an alkyl group); X each independently represents a single bond or a linking group (preferably a single bond, an alkylene group or -O-) Z' is each independently a monocyclic non-aromatic ring that may have a substituent, an aromatic ring that may have a substituent, or a represents a good bridged ring (preferably an aromatic ring which may have a substituent, particularly preferably a benzene ring which may have a substituent); a is each independently an integer of 0 to 2; (preferably 0); b represents 0 or 1 (preferably 0); c represents 0 or an integer of 1 or more (preferably 0 or an integer from 1 to 5, more preferably 0); * indicates a binding site. ] is preferably present in the component (A) molecule. Note that the a units and c units may be the same or different.

In the present specification, examples of "linking group" include alkylene group, alkenylene group, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, - Examples include COO-, -OCO-, and the like. In the present specification, "aromatic ring" includes not only a monocyclic aromatic ring and a condensed aromatic ring in which two or more monocyclic aromatic rings are fused, but also one or more monocyclic aromatic rings. It also includes fused aromatic rings in which one or more monocyclic non-aromatic rings are fused to , for example, monocyclic aromatic rings (preferably 5 or 6 members) such as benzene ring and pyridine ring, indane ring, fluorene ring. , a fused aromatic ring (preferably 8 to 14 members) such as a naphthalene ring, and the like. The aromatic ring may be a carbocycle or a heterocycle, but in one embodiment, a carbocycle is preferable.

The alkylene group refers to a straight or branched chain divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms. Examples of the alkylene group include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, and decamethylene group; ethylidene group (-CH(CH ₃ )-), propylidene group (-CH(CH ₂ CH ₃ )-), isopropylidene group (-C(CH ₃ ) ₂ -), ethylmethylmethylene group (-C(CH ₃ )( CH ₂ CH ₃ )-), diethylmethylene group (-C(CH ₂ CH ₃ ) ₂ -), 2-methyltetramethylene group, 2,3-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2 -Methylpentamethylene group, 2,2-dimethylpentamethylene group, 2,4-dimethylpentamethylene group, 1,3,5-methylpentamethylene group, 2-methylhexamethylene group, 2,2-dimethylhexamethylene group , 2,4-dimethylhexamethylene group, 1,3,5-trimethylhexamethylene group, 2,2,4-trimethylhexamethylene group, branched chain alkylene group such as 2,4,4-trimethylhexamethylene group, etc. can be mentioned. An alkenylene group refers to a straight or branched chain divalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenylene group is preferably an alkenylene group having 2 to 14 carbon atoms. Examples of the alkenylene group include groups specifically exemplified as alkylene groups in which any carbon-carbon single bond is replaced with a carbon-carbon double bond.

(A) It is preferable that the molecule of the maleimide compound containing a bridged ring skeleton has two or more aromatic tetracarboxylic acid diimide skeletons, and the upper limit may be, for example, 40 or less, 20 or less.

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

The maleimide-terminated polyimide containing a cross-linked ring skeleton preferably has the formula (A):

[In the formula, n+1 A ¹ 's each independently represent, for example, two or more atoms (for example, 2 to 3000, 2 A divalent organic group (preferably a divalent ring (e.g., a bridged ring, a monocyclic non-aromatic ring, an aromatic ring)) consisting of ~1000, 2-100, 2-50 skeleton atoms each of the n ^A2 's independently represents, for example, two or more atoms (for example, 2 to 3000 atoms) selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (preferably carbon atoms); A tetravalent organic group (preferably containing a tetravalent ring (e.g., a bridged ring, a monocyclic non-aromatic ring, an aromatic ring) consisting of skeletal atoms of 2 to 1000, 2 to 100, 2 to 50) at least one of n+1 A ¹ and n A ² contains a bridged ring skeleton in the organic group; n is an integer of 1 or more (preferably 1 to 1); an integer of 100, more preferably an integer of 1 to 50, particularly preferably an integer of 1 to 20). ] It is a bismaleimide compound represented by. Note that the n units may be the same or different for each unit.

In one embodiment, the n ^A2s do not have a bridged ring skeleton in the organic group, and at least one of the n+1 ^A1s has a bridged ring skeleton in the organic group. It is preferable. In the preferred embodiment, the ratio of the number of A ^1s having a bridged ring skeleton to the total number of A ^1s (i.e. n+1) is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0. .3 or more.

In one embodiment, each of the n+1 A ¹ 's independently preferably has the formula (Y1):

[In the formula, Y ¹ each independently represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group, particularly preferably a methylene group); Z ¹ is a bridge that may have a substituent Bridged ring (preferably tricyclic bridged ring, more preferably tricyclo[5.2.1.0 ^2,6 ]decane ring (for example, bonded to two Y ¹ at the 3 or 4 position and the 8 or 9 position) )); * indicates a binding site. ] or a divalent group represented by formula (Y2):

[In the formula, Y ²¹ each independently represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group, particularly preferably an octamethylene group); Y ²² each independently represents a single bond or a linkage represents a group (preferably a single bond, an alkylene group or -O-); each ^Z2 independently represents a monocyclic non-aromatic ring which may have a substituent, or a group having no substituent; an aromatic ring that may have a substituent (preferably a monocyclic non-aromatic ring that may have a substituent, more preferably a monocycloalkane ring that may have a substituent, particularly preferably a monocycloalkane ring that may have a substituent) d represents 0 or an integer of 1 or more (preferably 0 or an integer from 1 to 5, more preferably 0); * represents a bonding site. ], and at least one of the n+1 A ¹ 's is a divalent group represented by formula (Y1). Note that the d units may be the same or different for each unit.

Specific examples of the divalent group represented by formula (Y1) include divalent groups represented by the following formula:

[In the formula, * indicates a binding site. ].

Specific examples of the divalent group represented by formula (Y2) include divalent groups represented by the following formula:

[In the formula, * indicates a binding site. ].

In one embodiment, each of the n A ² independently preferably has the formula (X):

[In the formula, Z is each independently a monocyclic non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent (preferably a substituent-free The other symbols are the same as those of formula (X'). ] It is a tetravalent group represented by.

Specific examples of the tetravalent group represented by formula (X) include tetravalent groups represented by the following formula:

[In the formula, * indicates a binding site. ].

In one embodiment, (A) the maleimide compound containing a bridged ring skeleton preferably has the formula (A1):

[In the formula, n1 represents an integer of 1 or more (preferably an integer of 1 to 20, more preferably an integer of 1 to 10, particularly preferably an integer of 1 to 5); n2 is an integer of 0 or 1 or more (preferably an integer of 1 to 20, more preferably an integer of 1 to 10, particularly preferably an integer of 1 to 5); one of m1 and m2 is 1 and the other is 0 (preferably (indicates that m2 is 1 and m1 is 0); other symbols are the same as in formulas (X'), (Y1), (Y2), and (X). ] A bismaleimide compound (the bond between the n1 unit and the n2 unit is a bond) represented by the formula (A2) is more preferable:

[In the formulas, each symbol is the same as in formulas (X'), (Y1), (Y2), (X) and (A1). ], more preferably a bismaleimide compound represented by formula (A3):

[In the formula, R ² each independently represents an alkyl group (preferably a hexyl group or an octyl group); y1 each independently represents an integer of 0 to 14 (preferably 0 to 3, particularly preferably 1); y2 each independently represents an integer of 0 to 14 (preferably 3 to 14, more preferably 6 to 10, particularly preferably 8); z represents an integer of 0 to 3 (preferably represents 1 or 2, particularly preferably 2); other symbols are the same as in formula (A1). ], particularly preferably a bismaleimide compound represented by formula (A4):

[In the formula, each symbol is the same as in formula (A1). ] It is a bismaleimide compound represented by. In formulas (A1) to (A4), the order and individual arrangement of n1 units and n2 units are not particularly limited, and include alternating copolymers, block copolymers, random copolymers, and the like. Moreover, the n1 unit and the n2 unit may be the same or different for each unit.

(A) The weight average molecular weight (Mw) of the maleimide compound containing a crosslinked ring skeleton is preferably 2,000 to 50,000, more preferably 2,500 to 40,000, and even more preferably 3,000 to 20,000. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

(A) The functional group equivalent of the maleimide group of the maleimide compound containing a crosslinked ring skeleton is preferably 500 g/eq. ～20000g/eq. , more preferably 1000g/eq. ～10000g/eq. It is. The functional group equivalent of the maleimide group is the mass of the maleimide compound per equivalent of the maleimide group.

(A) Commercially available maleimide compounds containing a cross-linked ring skeleton include, for example, "BMI-2500" (bismaleimide compound of the above formula (A4)) manufactured by Designer Molecules.

The content of (A) the maleimide compound containing a crosslinked ring skeleton in the resin composition is not particularly limited, but is preferably 50% by mass when the nonvolatile components in the resin composition are 100% by mass. % or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less. The lower limit of the content of (A) the maleimide compound containing a crosslinked ring skeleton in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is preferably The content is 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 7% by mass or more.

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

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

As the other radically polymerizable compound (A'), a wide range of known radically polymerizable compounds can be used, and there are no particular limitations, such as (A'-1) other than the component (A). Examples include maleimide-based radically polymerizable compounds, (A'-2) vinylphenyl-based radically polymerizable compounds, and (A'-3) (meth)acrylic-based radically polymerizable compounds.

<(A'-1) Maleimide radically polymerizable compound>
(A'-1) The maleimide-based radically polymerizable compound is a compound other than component (A), and is an organic compound containing one or more (preferably two or more) maleimide groups in one molecule. . (A'-1) Maleimide-based radically polymerizable compounds may be used alone or in combination of two or more in any ratio. (A'-1) Maleimide-based radically polymerizable compound includes, for example, (A'-1-1) maleimide-terminated polyimide other than component (A), (A'-1-2) aromatic maleimide compound, and (A'-1-2) aromatic maleimide compound; '-1-3) It is preferable to contain at least one maleimide compound selected from aliphatic maleimide compounds.

<(A'-1-1) Maleimide-terminated polyimide>
(A'-1-1) Maleimide-terminated polyimide is a chain polyimide that does not contain a cross-linked ring skeleton and has maleimide groups at both ends. (A'-1-1) Maleimide-terminated polyimide may be a component that can be obtained by, for example, subjecting a component containing a diamine compound, maleic anhydride, and tetracarboxylic dianhydride to an imidization reaction.

In one embodiment, (A'-1-1) maleimide-terminated polyimide has the formula (B):

[In the formula, n+1 B ¹ 's are each independently, for example, two or more atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (for example, 2 to 3000 atoms, 2 to 1000 atoms, 2 to 1000 atoms, A divalent organic group (preferably an organic group containing a divalent ring (e.g., monocyclic non-aromatic ring, aromatic ring)) consisting of skeletal atoms (preferably carbon atoms) of 100 or 2 to 50 atoms. ; n ^B2 's are each independently, for example, two or more atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms (for example, 2 to 3000 atoms, 2 to 1000 atoms, 2 to 100 atoms, A tetravalent organic group (preferably an organic group containing a tetravalent ring (e.g., a monocyclic non-aromatic ring, an aromatic ring, preferably an aromatic ring)) consisting of 2 to 50 skeleton atoms (preferably carbon atoms) n+1 B ¹ and n B ² do not contain a bridged ring skeleton in the organic group; n is an integer of 1 or more (preferably an integer of 1 to 100, more preferably (an integer of 1 to 50, particularly preferably an integer of 1 to 20). ] It is a bismaleimide compound represented by. Note that the n units may be the same or different for each unit.

In one embodiment, (A'-1-1) maleimide-terminated polyimide preferably has the formula (B1):

[In the formula, Y ³¹ each independently represents a single bond, an alkylene group, or an alkenylene group; Y ³² each independently represents a single bond or a linking group; Z ³ each independently represents Represents a monocyclic non-aromatic ring that may have a substituent or an aromatic ring that may have a substituent; e represents an integer of 0 or 1 or more; Other symbols are represented by the formula ( X) and formula (X'). ] It is a bismaleimide compound represented by.

(A'-1-1) The weight average molecular weight (Mw) of the maleimide-terminated polyimide is preferably 500 to 50,000, more preferably 1,000 to 20,000.

(A'-1-1) The functional group equivalent of the maleimide group of the maleimide-terminated polyimide is preferably 300 g/eq. ～20000g/eq. , more preferably 500g/eq. ～10000g/eq. It is.

(A'-1-1) Commercially available maleimide-terminated polyimides include, for example, "BMI-1500", "BMI-1700", and "BMI-3000J" manufactured by Designer Molecules.

<(A'-1-2) Aromatic maleimide compound>
(A'-1-2) Aromatic maleimide compound is a maleimide compound that does not fall under the components (A) and (A'-1-1), and contains one or more aromatic rings in one molecule. And it means a maleimide compound containing two or more maleimide groups. In one embodiment, the aromatic maleimide compound (A'-1-2) may be an addition-polymerized aromatic maleimide. (A'-1-2) Aromatic maleimide compound is a maleimide compound having one aromatic ring such as N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, etc. Although it may be a maleimide compound having two or more aromatic rings, it is preferably a maleimide compound having two or more aromatic rings.

In one embodiment, the aromatic maleimide compound (A'-1-2) has the formula (C):

[In the formula, R ^c each independently represents a substituent; X ^c each independently represents a single bond or a connecting group (preferably a single bond or an alkylene group); Z ^c each independently represents a substituent; A monocyclic non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent (preferably an aromatic ring which may have a substituent, particularly preferably s represents an integer of 1 or more; t each independently represents an integer of 0 or 1 or more; u each independently represents Indicates an integer from 0 to 2 (preferably 0). ], preferably formulas (C1-1) to (C1-4):

[In the formula, R ^c1 , R ^c2 and R ^c3 each independently represent an alkyl group; X ^c1 and X ^c2 each independently represent a single bond or an alkylene group; s is one or more represents an integer (preferably an integer of 1 to 100, more preferably an integer of 1 to 50, still more preferably an integer of 1 to 20); t' represents an integer of 1 to 5; u1, u2 and u3 are Each independently represents an integer of 0 to 2 (preferably 0). ] It is a maleimide compound represented by. Note that the s unit, t unit, t' unit, u unit, u1 unit, u2 unit, and u3 unit may be the same or different for each unit.

(A'-1-2) The functional group equivalent of the maleimide group of the aromatic maleimide compound is preferably 50 g/eq. ～2000g/eq. , more preferably 100g/eq. ～1000g/eq. More preferably 150g/eq. ～700g/eq. , particularly preferably 200 g/eq. ～500g/eq. It is.

(A'-1-2) Commercially available aromatic maleimide compounds include, for example, "MIR-3000-70MT" (biphenylaralkyl novolac type polymerimide) manufactured by Nippon Kayaku Co., Ltd.; "BMI-50P" manufactured by KI Kasei Co., Ltd. "; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100" manufactured by Daiwa Kasei Industries; "BMI-5100" manufactured by KI Kasei Co., Ltd. -4,4'-BPE'', ``BMI-70'', and ``BMI-80'' manufactured by KI Kasei Co., Ltd., etc.

<(A'-1-3) Aliphatic maleimide compound>
(A'-1-3) Aliphatic maleimide compound refers to an aliphatic maleimide compound that has a basic skeleton of a non-aromatic hydrocarbon (preferably 2 to 50 carbon atoms) and has two or more (preferably two) maleimides in one molecule. It is a compound that has a group.

In one embodiment, the (A'-1-3) aliphatic maleimide compound has the formula (D):

[wherein, X ^d each independently represents a single bond, an alkylene group or an alkenylene group (preferably an alkylene group or an alkenylene group); Z ^d is each independently selected from an alkyl group and an alkenyl group represents a monocyclic non-aromatic ring which may have a group (preferably a monocycloalkane ring or monocycloalkene ring which may have a group selected from an alkyl group and an alkenyl group); Indicates an integer of 0 or 1 or more (preferably an integer of 1 or more, particularly preferably 1). ] It is a maleimide compound represented by. Note that x units may be the same or different for each unit.

(A'-1-3) Specific examples of aliphatic maleimide compounds include linear aliphatic bismaleimide compounds; 1-maleimido-3-maleimidomethyl-3,5,5-trimethylcyclohexane (IPBM), 1,1'-(cyclohexane-1,3-diylbismethylene)bis(1H-pyrrole- 2,5-dione) (CBM), 1,1'-(4,4'-methylenebis(cyclohexane-4,1-diyl))bis(1H-pyrrole-2,5-dione) (MBCM), etc. Cyclic bismaleimide compounds; bismaleimides containing a dimer acid skeleton, and the like.

Dimer acid skeleton-containing bismaleimide refers to dimer acid with two terminal carboxy groups (-COOH) replaced by a maleimide group or a maleimidomethyl group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-ylmethyl group). ) means a bismaleimide compound substituted with Dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably one having 11 to 22 carbon atoms, particularly preferably one having 18 carbon atoms), and its industrial production process is almost universal in the industry. Standardized. Among the dimer acids, those whose main component is a dimer acid with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid and linoleic acid, which are inexpensive and easily available, are easily available. Further, the dimer acid may contain an arbitrary amount of monomer acid, trimer acid, other polymerized fatty acids, etc. depending on the manufacturing method, degree of purification, etc. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, dimer acids also include hydrogenated products in which the degree of unsaturation is reduced by further hydrogenation reaction.

(A'-1-3) The functional group equivalent of the maleimide group of the aliphatic maleimide compound is preferably 50 g/eq. ～2000g/eq. , more preferably 100g/eq. ～1000g/eq. More preferably 200g/eq. ～600g/eq. , particularly preferably 300g/eq. ～400g/eq. It is.

(A'-1-3) Commercially available aliphatic maleimide compounds include, for example, "BMI-689", "BMI-1500", and "BMI-3000J" manufactured by Designer Molecules.

<(A'-2) Vinylphenyl radically polymerizable compound>
(A'-2) Vinylphenyl-based radically polymerizable compound is a radically polymerizable compound having a vinylphenyl group. The vinyl phenyl radically polymerizable compound preferably has two or more vinyl phenyl groups per molecule.

In one embodiment, (A'-2) the vinyl phenyl-based radically polymerizable compound is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and has the formula (E-1):

[In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group). ]
(The number of repeating units is preferably 2 to 300, more preferably 2 to 100) and a vinylbenzyl-modified polyphenylene ether having a repeating unit represented by Particularly preferred is a polyphenylene ether modified with vinylbenzyl at both ends.

In another embodiment, (A'-2) the vinyl phenyl radically polymerizable compound has the formula (E-2):

[In the formula, R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom). ]
A divinylbenzene polymer having a repeating unit represented by (preferably the number of repeating units is 2 to 200) is preferable. The divinylbenzene polymer may also be a copolymer having other styrene skeleton units such as styrene units and ethylstyrene units. When other styrene skeletal units are included, the proportion of the repeating unit of formula (E-2) is preferably 5 to 70 mol % based on the total styrene skeletal units.

(A'-2) The number average molecular weight of the vinyl phenyl radically polymerizable compound is preferably 500 to 100,000, more preferably 700 to 80,000. (A'-2) The functional group equivalent of the vinyl group of the vinyl phenyl radically polymerizable compound is preferably 200 g/eq. ～3000g/eq. , more preferably 200g/eq. ～2000g/eq. It is.

(A'-2) Commercially available vinyl phenyl radically polymerizable compounds include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical; Examples include "ODV-XET-X03", "ODV-XET-X04", and "ODV-XET-X05" (divinylbenzene polymer) manufactured by Chemical & Materials Co., Ltd.

<(A'-3) (meth)acrylic radically polymerizable compound>
(A'-3) The (meth)acrylic radically polymerizable compound is a radically polymerizable compound having an acryloyl group and/or a methacryloyl group. (A'-3) The (meth)acrylic radically polymerizable compound preferably has two or more acryloyl groups and/or methacryloyl groups per molecule. (A'-3) The (meth)acrylic radically polymerizable compound is preferably a (meth)acrylic modified polyphenylene ether having an acryloyl group and/or a methacryloyl group and a polyphenylene ether skeleton, and has the formula (F):

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group). ]
(The number of repeating units is preferably 2 to 300, more preferably 2 to 100) and (meth)acrylic modified polyphenylene ether having an acryloyl group and/or a methacryloyl group (particularly a polyphenylene ether with both terminal hydroxyl groups) Particularly preferred is (meth)acrylic-modified polyphenylene ether in which hydrogen atoms are replaced with acryloyl groups and/or methacryloyl groups.

(A'-3) The number average molecular weight of the (meth)acrylic radically polymerizable compound is preferably 500 to 10,000, more preferably 700 to 5,000. (A'-3) The functional group equivalent of the acryloyl group and methacryloyl group of the (meth)acrylic radically polymerizable compound is preferably 200 g/eq. ～3000g/eq. , more preferably 300g/eq. ～2000g/eq. It is.

(A'-3) Commercially available (meth)acrylic radically polymerizable compounds include, for example, "SA9000" and "SA9000-111" (methacrylic modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

The content of (A') other radically polymerizable compounds in the resin composition is not particularly limited, but is preferably 50% by mass or less when the nonvolatile components in the resin composition are 100% by mass. , more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less. The lower limit of the content of (A') other radically polymerizable compounds in the resin composition is not particularly limited, but when the nonvolatile components in the resin composition are 100% by mass, for example, 0 mass%. % or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, etc.

The content of (A) the maleimide compound containing a crosslinked ring skeleton in the resin composition is 100% by mass of all radically polymerizable compounds (the sum of components (A) and (A')) in the resin composition. If so, it is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more.

<(B) Active ester compound>
The resin composition of the present invention contains (B) an active ester compound. (B) The active ester compounds may be used alone or in combination of two or more in any ratio. In one embodiment, when the resin composition includes (C) an epoxy resin or when the resin composition is mixed with (C) an epoxy resin, the (B) active ester compound reacts with the (C) epoxy resin. (C) It may have the function of crosslinking the epoxy resin.

(B) Active ester compounds generally have two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having the following properties are preferably used. The active ester compound is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester compounds obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester compounds obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound are more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, Examples include benzenetriol, dicyclopentadiene type diphenol compounds, and phenol novolacs. Here, the term "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, the active ester compound (B) includes a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolak. Active ester compounds are preferred, and among them, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred, and dicyclopentadiene-type active ester compounds are even more preferred. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable. "Dicyclopentadiene type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

(B) Commercially available active ester compounds containing a dicyclopentadiene diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "EXB-8000L-65M". ”, “EXB-8000L-65TM”, “HPC-8000L-65TM”, “HPC-8000”, “HPC-8000-65T”, “HPC-8000H”, “HPC-8000H-65TM”, (Manufactured by DIC ); "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T" as active ester compounds containing a naphthalene structure, "HPC-8150-62T" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester compound; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is an acetylated product of phenol novolak , "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds which are benzoylated products of phenol novolak, "PC1300-02-65MA" (air) as active ester compounds containing a styryl group and naphthalene structure・Manufactured by Water Co.), etc.

(B) The active ester group equivalent of the active ester compound is preferably 50 g/eq. ～500g/eq. , more preferably 50g/eq. ～400g/eq. , more preferably 100g/eq. ～300g/eq. It is. The active ester group equivalent is the mass of the active ester compound per equivalent of active ester group.

The content of the active ester compound (B) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably It is 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less. The lower limit of the content of the active ester compound (B) in the resin composition is not particularly limited, but is preferably 0.1% by mass or more when the nonvolatile components in the resin composition are 100% by mass. , more preferably 1% by mass or more, still more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 7% by mass or more.

The mass ratio of the (A) maleimide compound containing a crosslinked ring skeleton to the (B) active ester compound in the resin composition (component (A)/component (B)) is preferably 0.1 or more, more preferably It is 0.5 or more, particularly preferably 0.8 or more. The upper limit of the mass ratio (component (A)/component (B)) of the maleimide compound containing a crosslinked ring skeleton (A) to the active ester compound (B) in the resin composition is preferably 10 or less, more preferably It is 3 or less, particularly preferably 1.5 or less.

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

(C) Epoxy resins include, for example, 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, and trisphenol type epoxy resin. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, Cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phenolphthalein Examples include molded epoxy resins. (C) Epoxy resins may be used alone or in combination of two or more.

It is preferable that the resin composition contains, as the epoxy resin (C), an epoxy resin having two or more epoxy groups in one molecule. (C) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably is 70% by mass or more.

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

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

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 novolak type epoxy resin, and ester skeleton. Preferred are alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure.

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

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

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, phenolphthalyl Midine type epoxy resins and phenolphthalein type epoxy resins are preferred.

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

(C) When using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin/solid epoxy resin) is not particularly limited. However, it is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, even more preferably 0.5 or less, particularly preferably 0.1 or less.

(C) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ～5,000g/eq. , more preferably 60g/eq. ~2,000g/eq. , more preferably 70g/eq. ～1,000g/eq. , even more preferably 80 g/eq. ～500g/eq. It is. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin (C) 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 value in terms of polystyrene by gel permeation chromatography (GPC).

The content of the epoxy resin (C) in the resin composition is not particularly limited, but when the nonvolatile components in the resin composition are 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less. It is at most 40% by mass, more preferably at most 40% by mass, even more preferably at most 30% by mass, particularly preferably at most 20% by mass. The lower limit of the content of the epoxy resin (C) in the resin composition is not particularly limited, but is preferably 0% by mass or more, for example, when the nonvolatile components in the resin composition are 100% by mass. is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 1% by mass or more, even more preferably 5% by mass or more, particularly preferably 10% by mass or more. be.

The mass ratio of the (A) maleimide compound containing a crosslinked ring skeleton to the (C) epoxy resin in the resin composition (component (A)/component (C)) is preferably 0.1 or more, more preferably 0. .3 or more, particularly preferably 0.5 or more. The upper limit of the mass ratio (component (A)/component (C)) of the maleimide compound containing a crosslinked ring skeleton (A) to the epoxy resin (C) in the resin composition is preferably 10 or less, more preferably 3. Below, it is particularly preferably 1 or less.

<(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 contained in the resin composition in the form of particles.

(D) An inorganic compound is used as the material for the inorganic filler. (D) Materials for the inorganic filler include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, 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 suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (D) Inorganic fillers may be used alone or in combination of two or more in any ratio.

(D) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka; “Silfill NSS-3N”, “Silfill NSS-4N”, “Silfill NSS-” manufactured by Tokuyama Examples include "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatex; "DAW-03" and "FB-105FD" manufactured by Denka.

(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 0.5 μm or less. It is 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, particularly preferably 0. .2 μm or more. (D) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and using the median diameter as the average particle size. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler was measured using a flow cell method. The average particle size was calculated as the median diameter. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

(D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, even more preferably 1 m ² /g or more, Particularly preferably, it is 3 m ² /g or more. (D) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, even more preferably 50 m ² /g or less, particularly preferably is 40 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method. You can get it by doing that.

(D) The inorganic filler is preferably surface-treated with an appropriate surface treatment agent. The surface treatment can improve the moisture resistance and dispersibility of the inorganic filler (D). Examples of surface treatment agents include vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxy-based silane coupling agents; styryl-based such as p-styryltrimethoxysilane Silane coupling agent; methacrylic silane coupling agent such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N - Amino-based silane coupling agents such as phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; tris-(trimethoxysilylpropyl)isocyanurate, etc. Isocyanurate-based silane coupling agents; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. ; Isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; Acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; Silane coupling agents such as methyltrimethoxysilane; Dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane Examples include non-silane coupling alkoxysilane compounds such as ethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyltrimethoxysilane. Furthermore, the surface treatment agents may be used alone or in combination of two or more in any ratio.

Commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent); "KBM-303", "KBM-402", and "KBE-1003" manufactured by Shin-Etsu Chemical Co., Ltd. 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-based silane coupling agent); ``KBM-9659'' (isocyanurate-based silane coupling agent); "KBE-585" (ureide silane coupling agent); "KBM-802", "KBM-803" (mercapto silane coupling agent); "KBE-9007N" (isocyanate silane coupling agent); "X -12-967C” (acid anhydride silane coupling agent); “KBM-13”, “KBM-22”, “KBM-103”, “KBE-13”, “KBE-22”, “KBE-103” ", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( non-silane coupling (alkoxysilane compound), etc.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, and preferably 0.2% by mass to 3% by mass. It is more preferable that the surface is treated in an amount of 0.3% by mass to 2% by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in sheet form, the amount is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ² The following are more preferred.

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

The content of the inorganic filler (D) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is preferably 90% by mass or less, more preferably It may be 80% by weight or less, more preferably 75% by weight or less, particularly preferably 70% by weight or less. The lower limit of the content of the inorganic filler (D) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 1% by mass. % or more, preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more.

The mass ratio of the maleimide compound containing a crosslinked ring skeleton (A) to the inorganic filler (D) in the resin composition (component (A)/component (D)) is preferably 0.01 or more, more preferably It is 0.05 or more, particularly preferably 0.1 or more. The upper limit of the mass ratio (component (A)/component (D)) of the maleimide compound containing a crosslinked ring skeleton (A) to the inorganic filler (D) in the resin composition is preferably 1 or less, more preferably It is 0.5 or less, particularly preferably 0.3 or less.

<(E) Curing accelerator>
The resin composition of the present invention may contain (E) a curing accelerator as an optional component.

Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. (E) The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, and tetrabutylphosphonium hydro Aliphatic phosphonium salts such as denhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl Phosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 - Aromatic phosphonium salts such as methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl- Aliphatic phosphine such as 2-butenyl)phosphine, 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-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( Examples include aromatic phosphines such as diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. It will be done.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as 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, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea] etc.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide and the like.

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'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , imidazole compounds such as 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

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

Examples of the metal hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes such as , organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As the amine curing accelerator, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine Techno.

The content of the curing accelerator (E) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably It is 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less. The lower limit of the content of the curing accelerator (E) in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, for example, 0% by mass or more, 0% by mass. It may be .001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, etc.

<(F) Other additives>
The resin composition of the present invention may further contain arbitrary additives as nonvolatile components. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; phenolic curing agents, naphthol-based curing agents, acid anhydride-based curing agents, and thiols. Epoxy curing agents other than active ester compounds such as curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, imidazole curing agents; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, Thermoplastic resins such as ether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; Coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; silicone leveling agents, acrylic polymer leveling agents, etc. Leveling agents; Thickeners such as bentone and montmorillonite; Antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; Benzotriazole ultraviolet absorbers, etc. UV absorbers; adhesion improvers such as urea silane; adhesion agents such as triazole adhesion agents, tetrazole adhesion agents, triazine adhesion agents; hindered phenolic antioxidants, hindered amines Antioxidants such as antioxidants; Fluorescent brighteners such as stilbene derivatives; Surfactants such as fluorine surfactants and silicone surfactants; Phosphorus flame retardants (e.g. phosphate ester compounds, phosphazene compounds, Flame retardants such as 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); phosphate ester-based dispersants, polyoxyalkylene-based dispersants Dispersants such as acetylene dispersants, silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers Stabilizers such as carboxylic acid stabilizers, carboxylic acid anhydride stabilizers, and the like can be mentioned. (F) Other additives may be used alone or in combination of two or more in any ratio. (F) The content of other additives can be determined as appropriate by those skilled in the art.

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

In one embodiment, the content of the organic solvent (G) is not particularly limited, but when all components in the resin composition are 100% by mass, 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.

<Method for manufacturing resin composition>
The resin composition of the present invention can be prepared, for example, in an arbitrary preparation container by adding (A) a maleimide compound containing a cross-linked ring skeleton, (B) an active ester compound, and optionally (A') another radically polymerizable compound. (C) Epoxy resin as necessary, (D) Inorganic filler as necessary, (E) Curing accelerator as necessary, (F) Other additives as necessary, and ( G) It can be produced by adding and mixing organic solvents in any order and/or some or all at the same time. Further, in the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or throughout. In addition, during or after the addition and mixing process, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to uniformly disperse the resin composition. Moreover, simultaneously with stirring or shaking, defoaming may be performed under low pressure conditions such as under vacuum.

<Characteristics of resin composition>
The resin composition of the present invention includes (A) a maleimide compound containing a cross-linked ring skeleton, and (B) an active ester compound. By using such a resin composition, it is possible to obtain a cured product that has a low dielectric constant (Dk) and a dielectric loss tangent (Df), a high glass transition point (Tg), and excellent copper adhesion.

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

The cured product of the resin composition of the present invention may be characterized by a low dielectric constant (Dk). Therefore, in one embodiment, the dielectric constant (Dk) of the cured resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 5.0 or less, more preferably It can be 4.0 or less, more preferably 3.5 or less, particularly preferably 3.0 or less.

The cured product of the resin composition of the present invention may be characterized by a high glass transition point (Tg). Therefore, in one embodiment, the glass transition temperature (Tg) when measured as in Test Example 2 below is preferably 130°C or higher, more preferably 140°C or higher, even more preferably 150°C or higher, particularly preferably 160°C or higher. Temperatures can exceed ℃.

The cured product of the resin composition of the present invention may be characterized by excellent copper adhesion. Therefore, in one embodiment, the copper foil adhesion strength when measured in accordance with JIS C6481 as in Test Example 5 below is preferably 0.2 kgf/cm or more, more preferably 0.3 kgf/cm or more, and It is preferably 0.4 kgf/cm or more, particularly preferably 0.5 kgf/cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf/cm or less. In one embodiment, the copper plating peel strength calculated from the load when a copper plating conductor layer is formed on a cured product and the copper plating conductor layer is peeled off in the vertical direction as in Test Example 4 below is preferably can be 0.2 kgf/cm or more, more preferably 0.3 kgf/cm or more, even more preferably 0.35 kgf/cm or more, particularly preferably 0.4 kgf/cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf/cm or less.

In one embodiment, the cured product of the resin composition of the present invention may have a feature that the arithmetic mean roughness (Ra) of the surface after roughening treatment is low. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the surface of the cured product after the roughening treatment measured as in Test Example 3 below is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 170 nm. Below, it may be even more preferably 150 nm or less, 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.

<Applications of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulation purposes, particularly as a resin composition for forming an insulation layer. Specifically, a resin composition for forming an insulating layer (including a rewiring layer) formed on an insulating layer (a resin for forming an insulating layer for forming a conductor layer) is used. composition). Further, in a printed wiring board to be described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be used in sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulating materials, hole-filling resins, component embedding resins, etc. that require resin compositions. Can be used in a wide range of applications.

Further, 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 used as a rewiring formation layer as an insulating layer for forming a rewiring layer. It can also be suitably used as a resin composition (resin composition for forming a rewiring formation layer) and a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) The step of laminating a temporary fixing film on the base material,
(2) Temporarily fixing the semiconductor chip on the temporary fixing film,
(3) forming a sealing layer on the semiconductor chip;
(4) Peeling the base material and temporary fixing film from the semiconductor chip,
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled; and (6) Forming a rewiring layer as a conductive layer on the rewiring layer. Forming process

Moreover, since the resin composition of the present invention provides an insulating layer with good component embeddability, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

<Sheet-like laminated material>
Although the resin composition of the present invention can be used by applying it in the form of a varnish, it is generally preferable for industrial use to use it in the form of a sheet-like laminate material containing the resin composition.

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

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

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 50 μm or less, from the viewpoint of making the printed wiring board thinner and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film. Preferably it is 40 μm or less. 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.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

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

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

The surface of the support to be bonded to the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The support with a release layer may be a commercially available product, such as "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by Unitika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is in the said range.

In one embodiment, the resin sheet may further include an arbitrary layer as necessary. Examples of such an arbitrary layer include a protective film similar to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). It will be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet can be made, for example, by using a liquid resin composition as it is, or by preparing a resin varnish by dissolving the resin composition in an organic solvent, applying this onto a support using a die coater, and then drying it. It can be manufactured by forming a resin composition layer.

Examples of the organic solvent include those similar to the organic solvents described as components of the resin composition. One type of organic solvent may be used alone, or two or more types may be used in combination.

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

The resin sheet can be stored by winding it up into a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of making the printed wiring board thinner, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 μm or more.

Prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

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

The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). It can be suitably used for interlayer insulating layers of wiring boards).

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

A printed wiring board can be manufactured, for example, using the above-mentioned resin sheet by a method including the following steps (I) and (II).
(I) Step of laminating the resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) Forming an insulating layer by curing (e.g., thermosetting) the resin composition layer. process of doing

The "inner layer substrate" used in step (I) is a member that becomes a substrate of a printed wiring board, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. Further, the substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer board in which a conductor layer (circuit) is formed on one or both sides of the board is sometimes referred to as an "inner layer circuit board." Further, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and/or a conductive layer is further formed is also included in the "inner layer substrate" as referred to in the present invention. If the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for hot-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as "heat-pressing member") include a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), and the like. Note that, instead of pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0. The pressure is in the range of .29 MPa to 1.47 MPa, and the heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressure laminator.

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

The support may be removed between step (I) and step (II) or after step (II).

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

For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., 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 is 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

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

When manufacturing a printed wiring board, the following steps may be further carried out: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. Note that when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or during step (IV). IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductive layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

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

Step (III) is a step of drilling a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be determined as appropriate depending on the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, smear is also removed in this step (IV). The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions commonly used in forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid in this order.

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

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

Further, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and a commercially available product includes, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

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

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

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-chromium alloy, a copper-chromium alloy, etc.). nickel alloys and copper-titanium alloys). Among these, from the viewpoint of versatility in forming conductor layers, cost, ease of patterning, etc., monometallic layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, nickel-chromium alloys, copper, etc. An alloy layer of nickel alloy or copper/titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel/chromium alloy is more preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is more preferable. More preferred is a metal layer.

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

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

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 an insulating layer using a conventionally known technique such as a semi-additive method or a fully additive method. It is preferable to form by a method. An example of forming a conductor layer by a semi-additive method will be shown below.

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

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

Metal foil can be manufactured by a known method such as an electrolytic method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd.

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

Examples of semiconductor devices include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, televisions, etc.), vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.), and the like.

Hereinafter, the present invention will be specifically explained with reference to Examples. The present invention is not limited to these examples. In addition, in the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The temperature condition when there is no particular temperature specification is room temperature (25° C.).

<Example 1>
10 parts of a cross-linked ring skeleton-containing maleimide compound ("BMI-2500" manufactured by Designer Molecules), 18.3 parts of an active ester compound ("HPC-8150-60T" manufactured by DIC, toluene solution with a solid content of 60% by mass) 18 parts of naphthol aralkyl epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd.), spherical silica (Admatex) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) "SO-C2" manufactured by Shikoku Kasei Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² /g) 60 parts, imidazole curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole) ) were mixed and uniformly dispersed using a high-speed rotating mixer to prepare a resin composition.

<Example 2>
The amount of active ester compound (“HPC-8150-60T” manufactured by DIC Corporation, toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, and the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical Co., Ltd. & Materials Co., Ltd. "ESN-475V") was changed from 18 parts to 15 parts, and biphenylaralkyl novolac type polymerimide (Nippon Kayaku Co., Ltd. "MIR-3000-70MT", MEK with a solid content of 70%) was changed from 18 parts to 15 parts. A resin composition was prepared in the same manner as in Example 1, except that 5.7 parts of the toluene mixed solution) was further used.

<Example 3>
Maleimide compound A represented by the following formula (1) synthesized by the method described in Synthesis Example 1 of Japan Institute of Invention and Innovation Publication No. 2020-500211 (Mw/Mn=1.81, t''=1 .47 (mainly 1, 2 or 3)) MEK solution (70% by mass of non-volatile components) was prepared.

The amount of active ester compound (“HPC-8150-60T” manufactured by DIC Corporation, toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, and the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical Co., Ltd. Example 1 except that the amount of ESN-475V manufactured by & Materials Co., Ltd. was changed from 18 parts to 15 parts, and 5.7 parts of maleimide compound A (MEK solution with a solid content of 70%) was further used. A resin composition was prepared in the same manner.

<Example 4>
The amount of active ester compound (“HPC-8150-60T” manufactured by DIC Corporation, toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, and the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical Co., Ltd. & Materials Co., Ltd. "ESN-475V") was changed from 18 parts to 15 parts, and a vinylbenzylated terminal PPE compound (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St-2200" was mixed with toluene with a solid content of 65%). A resin composition was prepared in the same manner as in Example 1, except that 6.2 parts of the solution was further used.

<Example 5>
The amount of active ester compound (“HPC-8150-60T” manufactured by DIC Corporation, toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, and the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical Co., Ltd. & Materials Co., Ltd. "ESN-475V") was changed from 18 parts to 15 parts, and a methacrylate-terminated PPE compound (Sabic Innovative Plastics Co., Ltd. "SA9000-111", 50% solids solution in toluene) was added. A resin composition was prepared in the same manner as in Example 1, except that 8 parts (adjusted to ) were further used.

<Example 6>
The amount of active ester compound (“HPC-8150-60T” manufactured by DIC Corporation, toluene solution with a solid content of 60% by mass) was changed from 18.3 parts to 16.7 parts, and the amount of naphthol aralkyl type epoxy resin (Nippon Steel Chemical Co., Ltd. The amount of divinylbenzene/styrene copolymer ("ODV-XET-X04" manufactured by Nippon Steel Chemical & Materials, solid content 65%) was changed from 18 parts to 15 parts. A resin composition was prepared in the same manner as in Example 1, except that 6.2 parts of the MEK/toluene mixed solution) was further used.

<Comparative example 1>
Except that 10 parts of aliphatic maleimide ("BMI-689" manufactured by Designer Molecules) was used instead of 10 parts of a cross-linked ring skeleton-containing maleimide compound ("BMI-2500" manufactured by Designer Molecules). A resin composition was prepared in the same manner as in Example 1.

<Comparative example 2>
Instead of 10 parts of a cross-linked ring skeleton-containing maleimide compound ("BMI-2500" manufactured by Designer Molecules), biphenylaralkyl novolac-type polymaleimide ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., solid content 70%) was used. A resin composition was prepared in the same manner as in Example 1, except that 14.3 parts of the MEK/toluene mixed solution) was used.

<Comparative example 3>
Instead of using 10 parts of a crosslinked ring skeleton-containing maleimide compound ("BMI-2500" manufactured by Designer Molecules), an active ester compound ("HPC-8150-60T" manufactured by DIC Corporation, a toluene solution with a solid content of 60% by mass) was used. ) was changed from 18.3 parts to 26.7 parts, and the amount of naphthol aralkyl epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Materials Co., Ltd.) was changed from 18 parts to 23 parts. A resin composition was prepared in the same manner as in Example 1.

<Comparative example 4>
Without using 18.3 parts of an active ester compound ("HPC-8150-60T" manufactured by DIC, a toluene solution with a solid content of 60% by mass), a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was used. The amount of surface-treated spherical silica ("SO-C2" manufactured by Admatex Corporation) was changed from 60 parts to 51 parts, and the amount of phenolic epoxy curing agent ("LA-7054" manufactured by DIC Corporation, solid content 60%) was changed from 60 parts to 51 parts. A resin composition was prepared in the same manner as in Example 1, except that 8.3 parts of MEK solution was further used.

<Test Example 1: Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)>
As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. The resin compositions obtained in 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. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

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

Regarding the cured product B for evaluation, the dielectric constant value (Dk value) and dielectric loss tangent were measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C using "HP8362B" manufactured by Agilent Technologies. The value (Df value) was measured. Measurements were performed on two test pieces, and the average was calculated.

<Test Example 2: Measurement of glass transition point (Tg)>
The resin sheet A obtained in Test Example 1 was cured in an oven at 190° C. for 90 minutes, and further peeled off from the support to obtain a cured film. This cured film was cut out to a length of 20 mm and a width of 6 mm and used as an evaluation sample. The glass transition temperature (Tg) of this evaluation sample was measured using a Rigaku TMA device from 25°C to 250°C at a heating rate of 5°C/min. Measurements were taken twice on the same specimen and the second value was recorded.

<Test Example 3: Measurement of arithmetic mean roughness (Ra)>
(1) Preparation of inner layer board Both sides of the glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) on which the inner layer circuit was formed are micro-coated. The copper surface was roughened by etching to a depth of 1 μm using an etching agent (“CZ8101” manufactured by MEC Corporation).

(2) Lamination of resin sheet A Using a batch vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator "CVP700"), test example 1 was carried out so that the resin composition layer was in contact with the inner layer substrate. The resin sheet A obtained in the above was laminated on both sides of the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then press-bonding at 120° C. and a pressure of 0.74 MPa for 30 seconds. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

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

(4) Roughening treatment The cured substrate A was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

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

(5) Measurement of the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment The arithmetic mean roughness (Ra) of the insulating layer surface of the cured substrate A after the roughening treatment was measured using a non-contact surface roughness meter. (WYKO NT3300 manufactured by Bruker) in VSI mode with a 50x lens and a measurement range of 121 μm x 92 μm. It was measured by calculating the average value of each 10 points.

<Test Example 4: Measurement of copper plating peel strength>
(1) Formation of copper-plated conductor layer A conductor layer was formed on the roughened surface of the insulating layer of the roughened cured substrate A obtained in Test Example 3 according to a semi-additive method. That is, the substrate after the roughening treatment was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then in an electroless copper plating solution at 25° C. for 20 minutes. Next, after performing an annealing treatment by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electrolytic 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 board will be referred to as "evaluation board B."

(2) Measurement of peel strength of copper-plated conductor layer The peel strength of the insulating layer and the conductor layer was measured in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a cut with a width of 10 mm and a length of 100 mm is made in the conductor layer of evaluation board B, one end of which is peeled off, gripped with a grip, and cut vertically at a speed of 50 mm/min at room temperature. The load (kgf/cm) when 35 mm was peeled off was measured to determine the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

<Test Example 5: Measurement of copper foil adhesion strength>
(1) Surface treatment of copper foil The shiny surface of “3EC-III” (electro-field copper foil, 35 μm) manufactured by Mitsui Mining & Mining Co., Ltd. is immersed in a micro-etching agent (“CZ8101” manufactured by MEC Co., Ltd.) to coat the copper surface. was subjected to roughening treatment (Ra value = 1 μm) and rust prevention treatment (CL8300). This copper foil is called CZ copper foil. Furthermore, it was heat-treated in an oven at 130°C for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer An inner layer substrate on which resin sheet A was laminated was prepared in the same manner as in Test Example 1. Thereafter, the supports on both sides were peeled off from the substrate to expose both resin composition layers. On these resin composition layers, the treated surface of CZ copper foil of "3EC-III" was laminated under the same conditions as the lamination of resin sheet A of Test Example 1. Then, a sample was prepared by curing the resin composition layer under curing conditions of 190° C. for 90 minutes to form an insulating layer.

(3) Measurement of copper foil peel strength (substrate adhesion) The prepared sample was cut into small pieces of 150 x 30 mm. Use a cutter to make a cut with a width of 10 mm and a length of 100 mm in the copper foil part of the small piece, peel off one end of the copper foil, and grasp it with a grip ("AC-50C-SL" manufactured by TSE Co., Ltd.). Using an Instron universal testing machine, the load [kgf/cm (N/cm)] when peeling off 35 mm in the vertical direction at a speed of 50 mm/min at room temperature was measured in accordance with JIS C6481. did.

The amounts of nonvolatile components used in the resin compositions of Examples and Comparative Examples and the measurement results of Test Examples are shown in Table 1 below.

As described above, by using a resin composition containing (A) a maleimide compound containing a cross-linked ring skeleton and (B) an active ester compound, the dielectric constant (Dk) and dielectric loss tangent (Df) are low, and the glass It was found that a cured product having a high transition point (Tg) and excellent copper adhesion could be obtained.

Claims (16)

(A) Maleimide compound containing a cross-linked ring skeleton, (B) active ester compound, (C) epoxy resin, (D) inorganic filler, and (A'-2) vinyl phenyl radically polymerizable compound and/or (A'-3) Contains a (meth)acrylic radically polymerizable compound,
The content of component (A) is 5 % by mass to 30% by mass when the nonvolatile components in the resin composition are 100% by mass,
The content of component (B) is 5 % by mass to 30% by mass, when the nonvolatile components in the resin composition are 100% by mass,
The content of component (C) is 5% by mass to 30 % by mass when the nonvolatile components in the resin composition are 100% by mass,
The content of component (D) is 50% by mass to 80 % by mass when the nonvolatile components in the resin composition are 100% by mass,
The content of the component (A'-2) is 0% by mass to 10% by mass when the nonvolatile components in the resin composition are 100% by mass,
A resin composition in which the content of component (A'-3) is 0% by mass to 10% by mass, when the nonvolatile components in the resin composition are 100% by mass . The resin composition according to claim 1, wherein the bridged ring in component (A) is a tricyclic bridged ring. The resin composition according to claim 2, wherein the tricyclic bridge ring is a tricyclo[5.2.1.0 ^2,6 ]decane ring. The resin composition according to any one of claims 1 to 3, wherein the number of maleimide groups in one molecule of component (A) is 2. The resin composition according to any one of claims 1 to 4, wherein component (A) is a maleimide-terminated polyimide containing a cross-linked ring skeleton. The resin composition according to any one of claims 1 to 5, wherein component (A) further contains an aromatic tetracarboxylic acid diimide skeleton. The resin composition according to any one of claims 1 to 6, wherein component (A) further contains a monocyclic non-aromatic ring skeleton. Component (A) is represented by formula (A1):

[In the formula, R ¹ each independently represents a substituent; X and Y ²² each independently represent a single bond or a linking group; Y ¹ and Y ²¹ each independently represent a single bond; represents a bond, an alkylene group, or an alkenylene group; Z and ^Z2 each independently represent a monocyclic non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent. ; Z ¹ each independently represents a bridged ring which may have a substituent; a each independently represents an integer of 0 to 2; b each independently represents , 0 or 1; c, d and n2 each independently represent 0 or an integer of 1 or more; n1 represents an integer of 1 or more; m1 and m2, one of which represents 1; And the other one shows 0. ]
The resin composition according to any one of claims 1 to 7, which is a bismaleimide compound represented by: The resin composition according to any one of claims 1 to 8, wherein component (A) has a weight average molecular weight of 2,000 to 50,000. The resin composition according to any one of claims 1 to 9, wherein the content of component (A) is 50% by mass or more when the total radically polymerizable compound in the resin composition is 100% by mass. . The resin composition according to any one of claims 1 to 10, wherein the mass ratio of component (A) to component (B) (component (A)/component (B)) is 0.5 to 3. A cured product of the resin composition according to any one of claims 1 to 11. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 11. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 11 provided on the support. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 11. A semiconductor device comprising the printed wiring board according to claim 15.