Resin composition

Abstract

To provide a resin composition which can obtain a cured product excellent in elongation characteristics and plating adhesion; a resin sheet containing the resin composition; a cured product of the resin composition; a circuit board including the cured product; and a semiconductor device including the circuit board.SOLUTION: A resin composition contains (A) a polystyrene resin having a radical polymerizable group at its side chain and having a molecular weight of less than 50,000, (B) a maleimide resin (excluding the component (A)), (C) an epoxy resin, and (D) a curing agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition. Further, it relates to a cured product, a resin sheet, a circuit board, and a semiconductor device obtained using the resin composition.

Background Art

[0002] Circuit boards such as printed wiring boards are widely used in various electronic devices. As a manufacturing technique for circuit boards, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer substrate is known. With the increasing functionality of electronic devices, the number of layers built up by circuit boards tends to increase. However, in order to increase the mechanical strength of the circuit board itself as the number of layers increases, excellent mechanical strength such as elongation characteristics has been demanded. As a resin composition having excellent elongation characteristics (elongation at break), a resin composition containing a styrene-based elastomer is known (Patent Documents 1 and 2).

[0003] Also, as a technique capable of obtaining a cured product having excellent adhesion, various resin compositions have been known so far (Patent Documents 3 to 7).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Summary of the Invention

Problems to be Solved by the Invention

[0005] When forming an insulating layer using a cured product of a resin composition and forming a conductor layer (wiring layer) on the insulating layer, generally, high adhesion between the insulating layer and the conductor layer is required. Regarding a resin composition containing a styrene-based elastomer, when an insulating layer is formed using the resin composition, it is difficult to obtain sufficient adhesion while maintaining excellent elongation properties, and further improvement is required.

[0006] The present invention was devised in view of the above problems, and aims to provide a resin composition capable of obtaining a cured product excellent in elongation properties and plating adhesion; a resin sheet containing the resin composition; a cured product of the resin composition; a circuit board containing the cured product; and a semiconductor device containing the circuit board.

Means for Solving the Problems

[0007] As a result of intensive studies on the above problems, the present inventors have found that by using a resin composition containing a combination of a polystyrene resin having a specific functional group and molecular weight, a maleimide resin, an epoxy resin, and a curing agent, a cured product excellent in elongation properties and plating adhesion can be obtained, and thus the present invention has been completed.

[0008] That is, the present invention includes the following. <1> (A) A polystyrene resin having a radically polymerizable group in the side chain and a molecular weight of less than 50,000, (B) a maleimide resin (excluding those corresponding to component (A)), (C) an epoxy resin, and (D) a curing agent, a resin composition. <2> The resin composition according to <1>, wherein component (A) has a radically polymerizable group selected from a (meth)acryloyl group and a vinylbenzyl group in the side chain. <3> The resin composition according to <1> or <2>, wherein the component (A) has a styrene unit which may have a substituent (excluding a radically polymerizable group) on the benzene ring, a styrene unit having a radically polymerizable group on the benzene ring and / or a vinyl unit having a radically polymerizable group (excluding the unit (a2)). <4> The resin composition according to <3>, wherein the amount of the styrene unit which may have a substituent (excluding a radically polymerizable group) on the benzene ring in the component (a1) is 70% by mass or more based on 100% by mass of the component (A). <5> The resin composition according to any one of <1> to <4>, wherein the component (A) has a structural unit represented by the following formula (A1) and has a structural unit represented by the following formula (A2) and / or the following formula (A3).

Chemical formula

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a resin composition capable of obtaining a cured product excellent in elongation characteristics and plating adhesion; a resin sheet containing the resin composition; a cured product of the resin composition; a circuit board containing the cured product; and a semiconductor device containing the circuit board.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0011] [Explanation of Terms] In this specification, the term "optionally substituted" for a compound or a group means both the case where a hydrogen atom of the compound or group is not substituted with a substituent and the case where some or all of the hydrogen atoms of the compound or group are substituted with a substituent.

[0012] In this specification, a substituent may further have a substituent (sometimes referred to as a "secondary substituent").

[0013] In this specification, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, etc.

[0014] In this specification, the term "alkyl group" refers to a linear, branched or cyclic monovalent aliphatic saturated hydrocarbon group. The number of carbon atoms of the alkyl group is preferably 1 to 14, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a tert-octyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, etc.

[0015] As used herein, the term "alkenyl group" refers to a linear, branched or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. The number of carbon atoms in the alkenyl group is preferably from 2 to 14, more preferably from 2 to 10, still more preferably from 2 to 6, and particularly preferably from 2 to 3. Examples of the alkenyl group include a vinyl group, a propenyl group (allyl group, 1-propenyl group, isopropenyl group), a butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.), a pentenyl group (1-pentenyl group, etc.), a hexenyl group (1-hexenyl group, etc.), a heptenyl group (1-heptenyl group, etc.), an octenyl group (1-octenyl group, etc.), a cyclopentenyl group (2-cyclopentenyl group, etc.), a cyclohexenyl group (3-cyclohexenyl group), and the like.

[0016] As used herein, the term "aryl group" refers to a monovalent aromatic hydrocarbon group. The number of carbon atoms in the aryl group is preferably from 6 to 14, more preferably from 6 to 10. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like.

[0017] As used herein, the term "aralkyl group" refers to an alkyl group substituted with one or more aryl groups. The number of carbon atoms in the aralkyl group is preferably from 7 to 15, more preferably from 7 to 11. Examples of the aralkyl group include a benzyl group, a phenethyl group, a hydrocinnamyl group, an α-methylbenzyl group, an α-cumyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and the like.

[0018] As used herein, the term "alkylaryl group" refers to an aryl group substituted with one or more alkyl groups. The number of carbon atoms in the alkylaryl group is preferably from 7 to 15, more preferably from 7 to 11. Examples of the alkylaryl group include a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 4-ethylphenyl group, a 3-ethylphenyl group, a 2-ethylphenyl group, a 4-isopropylphenyl group, a 3-isopropylphenyl group, a 2-isopropylphenyl group, and the like.

[0019] In this specification, the term "aromatic ring" means a ring that follows Hückel's rule, where the number of electrons contained in the π electron system on the ring is 4p + 2 (p is a natural number). The aromatic ring may be an aromatic carbon ring composed only of carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring having, as ring-constituting atoms, in addition to carbon atoms, heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. An aromatic carbon ring is preferred for the aromatic ring. Further, the aromatic ring such as an aromatic carbon ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring. Preferable specific examples of the aromatic carbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc., more preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring.

[0020] In this specification, the term "non-aromatic ring" means a ring other than an aromatic ring having aromaticity throughout the ring. The non-aromatic ring may be a non-aromatic carbon ring composed only of carbon atoms as ring-constituting atoms, or a non-aromatic heterocyclic ring having, as ring-constituting atoms, in addition to carbon atoms, heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. A non-aromatic carbon ring is preferred for the non-aromatic ring. The non-aromatic ring may be a saturated ring or an unsaturated ring. The non-aromatic ring is preferably a 3- to 21-membered non-aromatic ring, more preferably a 4- to 17-membered non-aromatic ring, and even more preferably a 5- to 14-membered non-aromatic ring. Preferable specific examples of the non-aromatic ring (non-aromatic carbon ring) include monocyclic non-aromatic saturated carbon rings such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring; monocyclic non-aromatic unsaturated carbon rings such as a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclopentadiene ring, a cyclohexadiene ring; bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decalin ring), bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring (hydrindane ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[3.3.0]octane ring, bicyclo[3.3.1]nonane ring, tricyclo[5.2.1.0 2,6Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7 Decane ring (adamantane ring), tricyclo[6.2.1.0 2,7 Bicyclic or higher non-aromatic saturated carbon rings such as undecane rings; bicyclic or higher non-aromatic unsaturated carbon rings such as bicyclo[2.2.1]hept-2-ene ring (norbornene ring), bicyclo[2.2.2]oct-2-ene ring, bicyclo[4.4.0]dec-2-ene ring, etc. are included. The non-aromatic ring may be a non-aromatic ring having an aromatic ring condensed therein. Examples of the non-aromatic ring having an aromatic ring condensed therein include indane ring, indene ring, tetralin ring, 1,2-dihydronaphthalene ring, 1,4-dihydronaphthalene ring, fluorene ring, 9,10-dihydroanthracene ring, 9,10-dihydrophenanthrene ring, etc.

[0021] In this specification, the term “(meth)acrylic acid” includes acrylic acid, methacrylic acid, and combinations thereof. Further, the term “(meth)acryloyl group” includes acryloyl group, methacryloyl group, and combinations thereof. Further, the term “(meth)acrylate” includes acrylate, methacrylate, and combinations thereof.

[0022] In this specification, the “non-volatile component” of the resin composition refers to the components of the resin composition excluding the (I) solvent described later.

[0023] In this specification, the “resin component” of the resin composition refers to the components of the non-volatile components constituting the resin composition excluding the (E) inorganic filler described later.

[0024] [Overview of Resin Composition] The resin composition of the present invention contains (A) a polystyrene resin having a radically polymerizable group in the side chain and a molecular weight of less than 50,000, (B) a maleimide resin (however, excluding those corresponding to component (A)), (C) an epoxy resin, and (D) a curing agent. Note that the “(A) polystyrene resin having a radically polymerizable group in the side chain and a molecular weight of less than 50,000” as component (A) may hereinafter be referred to as “(A) specific polystyrene resin”. By containing the above components, the resin composition can obtain a cured product excellent in elongation characteristics and plating adhesion. Further, in one embodiment, the cured product of the resin composition of the present invention may have a low dielectric tangent and a low relative dielectric constant.

[0025] In addition to components (A) to (D), the resin composition of the present invention may further contain (E) an inorganic filler, (F) a curing accelerator, (G) a thermoplastic resin, (H) other additives, and (I) a solvent as required. Hereinafter, each component contained in the resin composition will be described in detail.

[0026] <(A) polystyrene resin having a radically polymerizable group in the side chain and a molecular weight of less than 50,000> The resin composition contains, as component (A), (A) specific polystyrene resin (that is, a polystyrene resin having a radically polymerizable group in the side chain and a molecular weight of less than 50,000). (A) Specific polystyrene resin may be used alone or in combination of two or more.

[0027] (A) Specific polystyrene resin has a radically polymerizable group in the side chain. Examples of the radically polymerizable group include unsaturated hydrocarbon groups such as vinyl group, allyl group, 1-propenyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group; α,β-unsaturated carbonyl groups such as (meth)acryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), and the like. Among them, (A) specific polystyrene resin preferably has a radically polymerizable group selected from (meth)acryloyl group and vinylbenzyl group in the side chain.

[0028] (A) The molecular weight of the specific polystyrene resin (when having a distribution, the weight-average molecular weight Mw) is less than 50,000, preferably 45,000 or less, more preferably 40,000 or less, and still more preferably 35,000 or less. The lower limit is not particularly limited, but can be, for example, 100 or more, 500 or more, 1,000 or more, etc.

[0029] (A) The specific polystyrene resin has, for example, (a1) a styrene unit which may have a substituent on the benzene ring (however, excluding radical polymerizable groups) (hereinafter sometimes referred to as "(a1) unit"), and (a2) a styrene unit having a radical polymerizable group on the benzene ring (hereinafter sometimes referred to as "(a2) unit") and / or (a3) a vinyl unit having a radical polymerizable group (hereinafter sometimes referred to as "(a3) unit"). Further, (A) the specific polystyrene resin may further have an arbitrary structural unit. However, it is preferable that (A) the specific polystyrene resin does not have an arbitrary structural unit.

[0030] (a1) In the unit, the substituents that the benzene ring of styrene may have are not particularly limited except for radical polymerizable groups. For example, a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R a , -COR a , -OR a , -SR a , -SOR a , -SO2R a , -NHR a , -NR a 2, -COOR a , -OCOR a , -CONH2, -CONHR a , -CONR a 2, -NHCOR a and other monovalent substituents such as. However, R a each independently represents a monovalent hydrocarbon group (however, excluding unsaturated hydrocarbon groups).

[0031] R aThe number of carbon atoms in the monovalent hydrocarbon group represented is preferably 1 to 50, more preferably 1 to 20. Also, R a The monovalent hydrocarbon group represented may have a cyclic structure or may not have a cyclic structure. R a Examples of the monovalent hydrocarbon group represented include an alkyl group, an aryl group, an aralkyl group, an alkylaryl group, and the like.

[0032] In the (a1) unit, as the substituent other than the radical polymerizable group in the benzene ring of styrene, a monovalent hydrocarbon group is preferable, an alkyl group and an aryl group are more preferable, and an alkyl group is even more preferable. Among them, in the (a1) unit, the benzene ring of styrene is preferably unsubstituted.

[0033] The amount of the (a1) unit is preferably 70% by mass or more, more preferably 75% by mass or more, even more preferably 80% by mass or more, preferably 100% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less with respect to 100% by mass of the (A) specific polystyrene resin.

[0034] In the (a2) unit, examples of the radical polymerizable group in the benzene ring of styrene include unsaturated hydrocarbon groups such as a vinyl group, an allyl group, a 1-propenyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a 2-vinylphenyl group, a 3-vinylphenyl group, and a 4-vinylphenyl group; α,β-unsaturated carbonyl groups such as a (meth)acryloyl group and a maleimide group. Among them, as the radical polymerizable group in the (a2) unit, one or more radical polymerizable groups selected from a vinyl group, an allyl group, a 1-propenyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a 2-vinylphenyl group, a 3-vinylphenyl group, and a 4-vinylphenyl group are preferable, and a vinyl group is more preferable.

[0035] The number of radical polymerizable groups in the (a2) unit is not particularly limited and can be 1 or more.

[0036] (a2) unit, the benzene ring of styrene may have substituents other than the radical polymerizable group. In the (a2) unit, examples of the substituents other than the radical polymerizable group that the benzene ring of styrene can have include, for example, a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R a , -COR a , -OR a , -SR a , -SOR a , -SO2R a , -NHR a , -NR a 2, -COOR a , -OCOR a , -CONH2, -CONHR a , -CONR a 2, -NHCOR a and other monovalent substituents such as (however, R a is as described above.). In the (a2) unit, as the substituent other than the radical polymerizable group that the benzene ring of styrene has, a monovalent hydrocarbon group is preferable, an alkyl group and an aryl group are more preferable, and an alkyl group is even more preferable. Among them, in the (a2) unit, it is preferable that the benzene ring of styrene does not have a substituent other than the radical polymerizable group.

[0037] (a2) The amount of the unit is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 6% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less with respect to 100% by mass of the (A) specific polystyrene resin.

[0038] In the (a3) unit, the radically polymerizable group may be directly bonded to the vinyl unit, or may be indirectly bonded via a divalent linking group. Examples of the divalent linking group include divalent hydrocarbon groups which may have a substituent, such as an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, and an arylene group which may have a substituent; a group represented by -C(=O)O-, a group represented by -C(=O)-, a group represented by -C(=O)NH-, a group represented by -NHC(=O)NH-, a group represented by -NHC(=O)O-, a group represented by -C(=O)-, a group represented by -S-, a group represented by -SO-, a group represented by -NH-, and groups formed by combining a plurality of these groups. However, in the divalent linking group, a phenylene group is excluded. Examples of the substituent which the divalent linking group may have include a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R a , -COR a , -OR a , -SR a , -SOR a , -SO2R a , -NHR a , -NR a 2, -COOR a , -OCOR a , -CONH2, -CONHR a , -CONR a 2, -NHCOR a and other monovalent substituents (however, R a is as described above). The "divalent linking group" is preferably a divalent hydrocarbon group which may have a substituent, and more preferably a divalent hydrocarbon group having no substituent. Among them, in the (a3) unit, it is even more preferable that the radically polymerizable group is directly bonded to the vinyl unit.

[0039] (a3) The radical polymerizable group possessed by the unit may be, for example, within the same range as the radical polymerizable group possessed by the (a2) unit. Among them, as the radical polymerizable group possessed by the (a3) unit, one or more radical polymerizable groups selected from (meth)acryloyl group and maleimide group are preferable, and (meth)acryloyl group is more preferable.

[0040] The number of the radical polymerizable groups possessed by the (a3) unit is not particularly limited and can be 1 or more.

[0041] The amount of the (a3) unit is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 4% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, based on 100% by mass of the (A) specific polystyrene resin.

[0042] (A) The specific polystyrene resin preferably has a structural unit represented by the following formula (A1) and further has a structural unit represented by the following formula (A2) and / or the following formula (A3). In the (A) specific polystyrene resin, the order of the structural unit represented by the formula (A1), the structural unit represented by the formula (A2), and the structural unit represented by the formula (A3) is arbitrary.

[0043]

Chemical formula

[0044] (In formulas (A1) to (A3), R 1 and R 3 each independently represent a substituent (however, excluding radical polymerizable groups); R 2 and R 4 each independently represent a radical polymerizable group; L represents a divalent linking group (however, excluding a phenylene group); x, y, and z each represent an integer of 1 or more; m1 represents 0 or an integer of 1 to 5; m2 represents an integer of 1 to 5; m3 represents an integer of 0 or an integer from 1 to 4, and satisfies the relationship of 1 ≤ m2 + m3 ≤ 5.)

[0045] In formula (A1), R 1 each independently represents a substituent (excluding radical polymerizable groups). Examples of such substituents include a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R a , -COR a , -OR a , -SR a , -SOR a , -SO2R a , -NHR a , -NR a 2, -COOR a , -OCOR a , -CONH2, -CONHR a , -CONR a 2, -NHCOR a and other monovalent substituents (where R a is as described above).)

[0046] In formula (A1), m1 represents an integer of 0 or an integer from 1 to 5. m1 is preferably an integer of 0 or from 1 to 3, more preferably 0 or 1, and even more preferably 0.)

[0047] In formula (A1), x represents an integer of 1 or more. x is preferably 2 or more, more preferably 3 or more, and preferably 400 or less, more preferably 350 or less.)

[0048] In formula (A2), R 2 each independently represents a radical polymerizable group. Examples of such radical polymerizable groups include unsaturated hydrocarbon groups such as vinyl group, allyl group, 1-propenyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group; α,β-unsaturated carbonyl groups such as (meth)acryloyl group, maleimide group, etc. Among them, R 2One or more radically polymerizable groups selected from a vinyl group, an allyl group, a 1-propenyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a 2-vinylphenyl group, a 3-vinylphenyl group, and a 4-vinylphenyl group are preferable, and a vinyl group is more preferable.

[0049] In formula (A2), R 3 each independently represents a substituent (however, excluding radically polymerizable groups). The substituent represented by R 3 can be within the same range as the substituent represented by R 1 in formula (A1).

[0050] In formula (A2), m2 represents an integer of 1 to 5.

[0051] In formula (A2), m3 represents 0 or an integer of 1 to 4 and satisfies the relationship 1 ≦ m2 + m3 ≦ 5. m3 is preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0.

[0052] In formula (A2), y represents an integer of 1 or more. y is preferably 2 or more, more preferably 3 or more, preferably 400 or less, and more preferably 350 or less.

[0053] In formula (A3), R 4 represents a radically polymerizable group. The radically polymerizable group can be within the same range as the radically polymerizable group represented by R 2 in formula (A2). Among them, R 4 is preferably one or more radically polymerizable groups selected from a (meth)acryloyl group and a maleimide group, and more preferably a (meth)acryloyl group.

[0054] In formula (A3), L represents a divalent linking group (excluding a phenylene group). Examples of the divalent linking group represented by L include a single bond, or a divalent group composed of one or more (e.g., 1 to 50, 1 to 30, 1 to 20, 1 to 10) skeletal atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the divalent group composed of one or more skeletal atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom include an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an arylene group which may have a substituent, an alkylarylene group which may have a substituent, a heteroarylene group which may have a substituent, -O-, -NH-, -NR b -, -CO-, -CS-, -SO-, -SO2-, -C(=O)O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, and a divalent group formed by combining a plurality of these. Here, R b represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of the substituent that the divalent linking group represented by L may have include a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c -, -COR c -, -OR c -, -SR c -, -SOR c -, -SO2R c -, -NHR c -, -NR c 2, -COOR c -, -OCOR c -, -CONH2, -CONHR c -, -CONR c 2, -NHCOR c and other monovalent substituents. However, R c represents a monovalent hydrocarbon group.

[0055] The number of carbon atoms of the monovalent hydrocarbon group represented by R c is preferably 1 to 50, more preferably 1 to 20. R cThe monovalent hydrocarbon group represented by may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group. Also, R c The monovalent hydrocarbon group represented by may have a cyclic structure or may not have a cyclic structure. R c Examples of the monovalent hydrocarbon group represented by include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylaryl group, and the like.

[0056] Among them, the divalent linking group represented by L is preferably a single bond, or an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an arylene group which may have a substituent, -O-, -NR b -, -CO-, -CS-, -SO-, -SO2-, and a divalent group formed by combining a plurality of these is more preferably a single bond, or an alkylene group which may have a substituent, an arylene group which may have a substituent, and a divalent group formed by combining a plurality of these, and even more preferably a single bond.

[0057] In formula (A3), z represents an integer of 1 or more. z is preferably 2 or more, more preferably 3 or more, preferably 600 or less, and more preferably 550 or less.

[0058] (A) The radical polymerizable group equivalent of the specific polystyrene resin is preferably 500 g / eq. or more, more preferably 1,000 g / eq. or more, and even more preferably 2,000 g / eq. or more, and the upper limit thereof is preferably 6,000 g / eq. or less, more preferably 5,000 g / eq. or less, and even more preferably 4,000 g / eq. or less. The radical polymerizable group equivalent is the mass of the (A) specific polystyrene resin per 1 molar equivalent of the radical polymerizable group.

[0059] (A) The specific polystyrene resin may be a commercially available product. Examples of commercially available products of the (A) specific polystyrene resin include, for example, "XPA-8255" and "XPA-8272" manufactured by Mitsui Chemicals, Inc. (polystyrene resin having an acryloyl group in the side chain); "ODV-XET-X03", "ODV-XET-X04", and "ODV-XET-X05" manufactured by Nippon Steel Chemical & Material Co., Ltd. (polystyrene resin having a vinylphenyl group in the side chain), etc.

[0060] When the content of the (A) specific polystyrene resin in the resin composition is based on 100% by mass of the non-volatile components in the (A) to (D) components, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more or 5% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, 23% by mass or less, or 21% by mass or less.

[0061] When the resin composition contains components other than the (A) to (D) components, the content of the (A) specific polystyrene resin in the resin composition, based on 100% by mass of the non-volatile components in the resin composition, is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.2% by mass or more or 1.4% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less.

[0062] When the resin composition contains components other than the (A) to (D) components, the content of the (A) specific polystyrene resin in the resin composition, based on 100% by mass of the resin components in the resin composition, is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.

[0063] <(B) Maleimide resin> The resin composition contains a (B) maleimide resin as the component (B). The (B) maleimide resin as the component (B) does not include those corresponding to the above-mentioned component (A). The (B) maleimide resin has one or more maleimide groups in one molecule. The (B) maleimide resin may be used alone or in combination of two or more.

[0064] (B) The maleimide resin may be an aromatic maleimide resin having a maleimide group directly bonded to an aromatic ring, or an aliphatic maleimide resin having no maleimide group directly bonded to an aromatic ring. When the (B) maleimide resin contains an aliphatic maleimide resin, the aliphatic maleimide resin preferably includes a maleimide resin having a carbon skeleton derived from dimer acid. When the (B) maleimide resin contains an aromatic maleimide resin, the aromatic maleimide resin preferably includes a maleimide resin having one or more skeletons selected from a biphenyl skeleton and an indane skeleton. Therefore, the (B) maleimide resin preferably includes a maleimide resin having one or more skeletons selected from a carbon skeleton derived from dimer acid, a biphenyl skeleton, and an indane skeleton.

[0065] The carbon skeleton derived from dimer acid means a carbon skeleton excluding the two terminal carboxy groups (-COOH) of dimer acid, or a carbon skeleton obtained by replacing the two terminal carboxy groups (-COOH) with methylene groups (-CH2-). Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those having 11 to 22 carbon atoms, more preferably those having 14 to 20 carbon atoms, particularly preferably those having 18 carbon atoms), and its industrial manufacturing process is almost standardized in the industry. Dimer acid is readily available, especially those mainly composed of dimer acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, which are inexpensive and easily available. In addition, dimer acid may contain an arbitrary amount of monomer acid, trimer acid, and other polymerized fatty acids depending on the manufacturing method, degree of purification, etc. Further, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrogenated products obtained by further hydrogenation reaction to reduce the degree of unsaturation are also included in dimer acid.

[0066] The maleimide resin having a carbon skeleton derived from dimer acid preferably contains a maleimide resin represented by the following formula (B1).

[0067] [Chemical formula]

[0068] (In formula (B1), n1 + 1 X's each independently represent a divalent organic group composed of 5 or more skeletal atoms selected from a carbon atom, a nitrogen atom (not forming an imide), an oxygen atom, and a sulfur atom and non-skeletal atoms selected from a hydrogen atom and a halogen atom, and at least 1 of the n + 1 X's represents a divalent hydrocarbon group derived from dimer acid; n1 Y's each independently represent a tetravalent organic group composed of 5 or more skeletal atoms selected from a carbon atom, a nitrogen atom (not forming an imide), an oxygen atom, and a sulfur atom and non-skeletal atoms selected from a hydrogen atom and a halogen atom; n1 represents an integer of 0 or 1 or more.)

[0069] In formula (B1), the n1 + 1 Xs are each independently a divalent organic group composed of 5 or more (preferably 5 to 200, more preferably 5 to 100, still more preferably 5 to 50) skeletal atoms selected from a carbon atom, a nitrogen atom (not forming an imide), an oxygen atom, and a sulfur atom, and non-skeletal atoms selected from a hydrogen atom and a halogen atom, and at least one of the n + 1 Xs represents a divalent hydrocarbon group derived from a dimer acid.

[0070] The divalent hydrocarbon group derived from a dimer acid means a divalent hydrocarbon group obtained by removing two terminal carboxy groups (-COOH) of the dimer acid, or a divalent hydrocarbon group obtained by replacing two terminal carboxy groups (-COOH) with a methylene group (-CH2-).

[0071] The n1 + 1 Xs may have a divalent organic group other than the divalent hydrocarbon group derived from a dimer acid, but when the n1 + 1 Xs are 100 mol%, it is preferable that 30 mol% or more of them are divalent hydrocarbon groups derived from a dimer acid, more preferably 60 mol% or more, still more preferably 90 mol% or more, and even more preferably all of the n1 + 1 Xs are divalent hydrocarbon groups derived from a dimer acid.

[0072] The divalent organic group other than the divalent hydrocarbon group derived from a dimer acid in the n1 + 1 Xs may be a divalent organic group having no aromatic ring or a divalent organic group having an aromatic ring.

[0073] In formula (B1), each of the n1 Ys independently represents a tetravalent organic group composed of 5 or more (preferably 5 to 200, more preferably 5 to 100, still more preferably 5 to 50) skeletal atoms selected from carbon atoms, nitrogen atoms (not forming imides), oxygen atoms and sulfur atoms, and non-skeletal atoms selected from hydrogen atoms and halogen atoms. The tetravalent organic group represented by Y may be a tetravalent organic group having no aromatic ring, or a tetravalent organic group having an aromatic ring.

[0074] In one embodiment, the tetravalent organic group represented by Y is preferably a tetravalent group selected from the following formulas (Y1) to (Y5).

[0075]

Chemical formula

[0076] (In formulas (Y1) to (Y5), ring Y 11 、ring Y 21 、ring Y 22 、ring Y 31 、ring Y 32 、ring Y 33 、ring Y 41 、ring Y 42 、ring Y 43 、ring Y 44 、ring Y 51 、ring Y 52 、ring Y 53 、ring Y 54 and ring Y 55 each independently represent an aromatic ring which may have a substituent, or a non-aromatic ring which may have a substituent; Y 2a 、Y 3a 、Y 3b 、Y 4a 、Y 4b 、Y 4c 、Y 5a 、Y 5b 、Y 5c and Y 5d each independently represent a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-; R y each independently represents a hydrogen atom, an alkyl group which may be substituted with a halogen atom, or two Rs bonded to the same carbon atom y combine together to form a non-aromatic ring which may have a substituent; * indicates a bonding site; The two bonding sites on the same ring represented by * are bonding sites with two adjacent carbon atoms on the ring respectively.)

[0077] In formulas (Y1) to (Y5), ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 each independently represents an aromatic ring which may have a substituent, or a non-aromatic ring which may have a substituent. These cyclic structures are preferably aromatic rings which may have a substituent, more preferably benzene rings which may have a substituent, and even more preferably benzene rings which may be substituted with an alkyl group.)

[0078] Ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55The substituents that can be had are not particularly limited, and examples thereof include a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c , -COR c , -OR c , -SR c , -SOR c , -SO2R c , -NHR c , -NR c 2, -COOR c , -OCOR c , -CONH2, -CONHR c , -CONR c 2, -NHCOR c and the like of monovalent substituents (however, R c is as described above.). is a valence group.

[0079] In formulas (Y1) to (Y5), Y 2a , Y 3a , Y 3b , Y 4a , Y 4b , Y 4c , Y 5a , Y 5b , Y 5c and Y 5d each independently represents a single bond, -C(R y )2-, -O-, -CO-, -S-, -SO-, -SO2-, -CONH-, or -NHCO-, and in one embodiment, preferably, a single bond, -C(R y )2-, or -O-.

[0080] R y each independently represents a hydrogen atom or an alkyl group which may be substituted with a halogen atom, or two Rs y bonded to the same carbon atom are combined together to form a non-aromatic ring which may have a substituent. The alkyl group may be the same as the alkyl group in R c . R yEach independently represents, preferably, a hydrogen atom or an alkyl group which may be substituted by a halogen atom; more preferably, a methyl group which may be substituted by a hydrogen atom or a halogen atom; even more preferably, a hydrogen atom, a methyl group or a trifluoromethyl group; particularly preferably, a hydrogen atom or a methyl group.

[0081] R y The substituents that [a certain entity] may have are not particularly limited. For example, they include a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c , -COR c , -OR c , -SR c , -SOR c , -SO2R c , -NHR c , -NR c 2, -COOR c , -OCOR c , -CONH2, -CONHR c , -CONR c 2, -NHCOR c and other monovalent substituents (wherein R c is as described above).

[0082] In formula (B1), n1 represents an integer of 0 or 1 or more, preferably an integer of 0 or 1 to 10, and more preferably 0.

[0083] The maleimide resin having a carbon skeleton derived from dimer acid may be used alone or in combination of two or more.

[0084] Commercially available products of the maleimide resin having a carbon skeleton derived from dimer acid include, for example, "BMI-689", "BMI-1500", "BMI-1700", "BMI-3000J" manufactured by Designer Molecules Inc., "SLK-6895-T90" manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0085] Examples of the aromatic maleimide resin include a maleimide resin represented by the formula (B2).

[0086]

Chemical formula

[0087] (In the formula (B2), R 10 each independently represents a hydrogen atom or an alkyl group which may be substituted with a halogen atom; ring D each independently represents an aromatic carbon ring which may have a substituent; n2 represents an integer of 1 or more; The n2 units may be the same or different for each unit.)

[0088] In the formula (B2), R 10 each independently represents a hydrogen atom or an alkyl group which may be substituted with a halogen atom. The alkyl group may be the same as the alkyl group in R c . R 10 each independently preferably represents a hydrogen atom or an alkyl group; more preferably represents a hydrogen atom or a methyl group; still more preferably represents a hydrogen atom.

[0089] In the formula (B2), ring D each independently represents an aromatic carbon ring which may have a substituent. The aromatic carbon ring may be the same as the aromatic carbon ring described in the section of the aromatic ring in ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 . Also, the "substituent" in ring D is, for example, in ring Y 11, ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 may be the same as the substituent in the "optionally substituted aromatic ring" in ring D. Ring D preferably represents a benzene ring which may have a substituent; more preferably, it represents a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group; particularly preferably, it represents an (unsubstituted) benzene ring.

[0090] In formula (B2), n2 represents an integer of 1 or more, and is preferably an integer of 1 to 10.

[0091] The maleimide resin having a biphenyl skeleton preferably contains a maleimide resin represented by the following formula (B3).

[0092] [Chemical formula]

[0093] (In formula (B3), R 20 each independently represents a hydrogen atom or an alkyl group which may be substituted with a halogen atom; Ring E, ring F and ring G each independently represent an optionally substituted aromatic carbocyclic ring; n3 represents an integer of 1 or more; The n3 units may be the same or different for each unit.)

[0094] In formula (B3), R 20 each independently represents a hydrogen atom or an alkyl group which may be substituted with a halogen atom. The alkyl group is R cIt may be the same as the alkyl group in []. R 20 Each is preferably independently a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0095] In formula (B3), ring E, ring F and ring G each independently represent an aromatic carbocyclic ring which may have a substituent. The aromatic carbocyclic ring is ring Y 11 , ring Y 21 , ring Y 22 , ring Y 31 , ring Y 32 , ring Y 33 , ring Y 41 , ring Y 42 , ring Y 43 , ring Y 44 , ring Y 51 , ring Y 52 , ring Y 53 , ring Y 54 and ring Y 55 It may be the same as the aromatic carbocyclic ring described in the item of the aromatic ring in []. Ring E, ring F and ring G are preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with a group selected from an alkyl group and an aryl group, and even more preferably a (unsubstituted) benzene ring.

[0096] The substituents that ring E, ring F and ring G may have are not particularly limited. For example, a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c , -COR c , -OR c , -SR c , -SOR c , -SO2R c , -NHR c , -NR c 2, -COOR c , -OCOR c , -CONH2, -CONHR c , -CONR c , -NHCOR c and other monovalent substituents (wherein R c is as described above).

[0097] In formula (B3), n3 represents an integer of 1 or more, and is preferably an integer of 1 to 10.

[0098] Examples of commercially available maleimide resins having a biphenyl skeleton include "MIR-3000-70MT", "MIR-5000-60T", etc. manufactured by Nippon Kayaku Co., Ltd.

[0099] The maleimide resin having a biphenyl skeleton may be used alone or in combination of two or more.

[0100] The maleimide resin having an indane skeleton preferably includes a maleimide resin represented by the following formula (B4).

[0101]

Chemical formula

[0102] (In formula (B4), R 30 each independently represents an alkyl group; ring H and ring I each independently represent an aromatic carbon ring which may have a substituent; n4 represents an integer of 1 or more; The n4 units may be the same or different for each unit.)

[0103] In formula (B4), R 30 each independently represents an alkyl group. R 30 is preferably a methyl group.

[0104] In formula (B4), ring H each independently represents an aromatic aromatic ring which may have a substituent. Ring H is preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with an alkyl group, and even more preferably a benzene ring substituted with an alkyl group.

[0105] In formula (B4), ring I each independently represents an aromatic ring which may have a substituent. Ring I is preferably a benzene ring which may have a substituent, more preferably a benzene ring which may be substituted with an alkyl group, and even more preferably an (unsubstituted) benzene ring.

[0106] The substituents that ring H and ring I may have are not particularly limited. For example, a halogen atom, -NO2, -CN, -COH, -OH, -SH, -NH2, -COOH, -R c , -COR c , -OR c , -SR c , -SOR c , -SO2R c , -NHR c , -NR c 2, -COOR c , -OCOR c , -CONH2, -CONHR c , -CONR c 2, -NHCOR c and other monovalent substituents such as (however, R c is as described above).

[0107] In formula (B4), n4 represents an integer of 1 or more, and is preferably an integer of 1 to 20.

[0108] The maleimide resin having an indane skeleton can be produced, for example, by using the method described in JP-Invention Association Publication Technical Report Publication No. 2020-500211 or a method analogous thereto.

[0109] The maleimide resin having an indane skeleton may be used alone or in combination of two or more.

[0110] (B) The maleimide group equivalent weight of the maleimide resin is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, still more preferably 150 g / eq. or more, 200 g / eq. or more, 250 g / eq. or more, or 300 g / eq. or more, and its upper limit is preferably 2,000 g / eq. or less, more preferably 1,000 g / eq. or less, still more preferably 800 g / eq. or less, 600 g / eq. or less, 500 g / eq. or less, or 450 g / eq. or less. The maleimide group equivalent weight is the mass of the (B) maleimide resin per 1 molar equivalent of the maleimide group.

[0111] (B) The molecular weight of the maleimide resin is preferably less than 5,000, more preferably less than 3,000, still more preferably less than 2,000, 1,500, 1,200, or 1,000, and its lower limit is not particularly limited, but can be, for example, 300 or more, 400 or more, 500 or more, etc.

[0112] When the non-volatile components in the components (A) to (D) are taken as 100% by mass, the content of the (B) maleimide resin in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, or 7% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, or 27% by mass or less.

[0113] When the non-volatile components in the components (A) to (D) are taken as 100% by mass, the total amount of the (A) specific polystyrene resin and the (B) maleimide resin in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, or 13% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, or 46% by mass or less.

[0114] When the resin composition contains components other than the components (A) to (D), the content of the (B) maleimide resin in the resin composition, when the non-volatile components in the resin composition are 100% by mass, is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more or 1.8% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less or 8% by mass or less.

[0115] When the resin composition contains components other than the components (A) to (D), the content of the (B) maleimide resin in the resin composition, when the resin components in the resin composition are 100% by mass, is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more or 7% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less or 26% by mass or less.

[0116] When the resin composition contains components other than the components (A) to (D), the total amount of the (A) specific polystyrene resin and the (B) maleimide resin in the resin composition, when the resin components in the resin composition are 100% by mass, is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more or 13% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less or 46% by mass or less.

[0117] The mass ratio of the (B) maleimide resin to the (A) specific polystyrene resin in the resin composition ((content of component (B)) / (content of component (A))) is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 0.7 or more or 0.8 or more, and preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less or 1.7 or less.

[0118] <(C) epoxy resin> The resin composition contains, as component (C), a (C) epoxy resin. The (C) epoxy resin as component (C) does not include those corresponding to the above-mentioned components (A) and (B). The (C) epoxy resin may be used alone or in combination of two or more kinds.

[0119] Examples of the (C) epoxy resin include bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak 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, glycidyl cyclohexane type epoxy resin, alkyldiglycidyl ether type epoxy resin, cresol novolak 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, phenolphthalimide type epoxy resin, etc. The epoxy resin may be used alone or in combination of two or more kinds.

[0120] The resin composition preferably contains, as component (C), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more with respect to 100% by mass of the (C) epoxy resin.

[0121] 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 may contain only a liquid epoxy resin as the component (C), only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. Among them, from the viewpoint of remarkably obtaining the effects of the present invention, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0122] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0123] Examples of the liquid epoxy resin 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, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenolphthalimide type epoxy resin, and alkyldiglycidyl ether type epoxy resin, with glycidyl cyclohexane type epoxy resin being more preferable.

[0124] Specific examples of the liquid epoxy resin include "HP-4032", "HP-4032-D", "HP-4032-SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YED216D" (alkyl diglycidyl ether-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used alone or in combination of two or more.

[0125] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, a solid epoxy resin having three or more epoxy groups in one molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0126] As the solid epoxy resin, a vixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a tetraphenylethane type epoxy resin are preferable, and a vixylenol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin are more preferable.

[0127] Specific examples of the solid epoxy resin include "HP-4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC-7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN-475V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN-485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000H", "YX4000HK" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR-991S" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like. These may be used alone or in combination of two or more.

[0128] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (C), their quantitative ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:50, more preferably 1:0.05 to 1:20, still more preferably 1:0.1 to 1:10, by mass ratio.

[0129] The epoxy equivalent of the epoxy resin (C) is preferably 50 g / eq. to 5,000 g / eq., more preferably 50 g / eq. to 3,000 g / eq., still more preferably 80 g / eq. to 2,000 g / eq., and even more preferably 110 g / eq. to 1,000 g / eq. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0130] The weight average molecular weight (Mw) of the epoxy resin (C) is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. The weight average molecular weight (Mw) of the epoxy resin (a) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

[0131] When the content of the epoxy resin (C) in the resin composition is based on 100% by mass of the non-volatile components in components (A) to (D), it is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more or 22% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less or 31% by mass or less.

[0132] When the resin composition contains components other than components (A) to (D), the content of the epoxy resin (C) in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more or 7% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less or 12% by mass or less, when the non-volatile components in the resin composition are 100% by mass.

[0133] When the resin composition contains components other than the components (A) to (D), the content of the (C) epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more or 23% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less or 33% by mass or less, based on 100% by mass of the resin components in the resin composition.

[0134] The mass ratio of the (C) epoxy resin to the (A) specific polystyrene resin in the resin composition ((content of component (C)) / (content of component (A))) is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.3 or more or 1.4 or more, and preferably 10.0 or less, more preferably 8.0 or less, still more preferably 6.0 or less or 5.8 or less.

[0135] <(D) curing agent> The resin composition contains a (D) curing agent as the component (D). The (D) curing agent as this component (D) does not include those corresponding to the above-mentioned components (A) to (C). The (D) curing agent may be used alone or in combination of two or more.

[0136] Examples of the (D) curing agent include active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. Among them, from the viewpoint of significantly obtaining the effects of the present invention, the (B) curing agent preferably contains one or more curing agents selected from active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, and carbodiimide-based curing agents.

[0137] As the active ester-based curing agent, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and an aromatic hydroxy compound is more preferred. As the carboxylic acid compound, either an aromatic carboxylic acid compound or an aliphatic carboxylic acid compound may be used, and examples thereof include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and their halides. As the aromatic hydroxy compound, for example, (i) a polyaddition reaction product of an unsaturated aliphatic cyclic compound containing two double bonds in one molecule and phenols, (ii) various bisphenol compounds, (iii) an aromatic polyol having two or more hydroxy groups bonded to a carbon atom on the aromatic ring, (iv) an aromatic monool having one hydroxy group bonded to a carbon atom on the aromatic ring, etc. may be mentioned. Examples of the polyaddition reaction product of an unsaturated aliphatic cyclic compound and phenols include polyaddition reaction products of unsaturated aliphatic cyclic compounds such as dicyclopentadiene, tetrahydroindene, norbornadiene, limonene, vinylcyclohexene, etc. and phenols which may have a substituent (for example, phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, etc.), and specifically, for example, dicyclopentadiene-phenols polyaddition products may be mentioned. Examples of the bisphenol compound include bisphenol A, bisphenol F, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol M, etc.Examples of the aromatic polyol having two or more hydroxy groups bonded to the carbon atoms on the aromatic ring include hydroquinone, resorcinol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, phenol novolak, and the like. Examples of the aromatic monool having one hydroxy group bonded to the carbon atom on the aromatic ring include phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, naphthol, methylnaphthol, dimethylnaphthol, ethylnaphthol, propylnaphthol, vinylnaphthol, allylnaphthol, phenylnaphthol, benzylnaphthol, halonaphthol, and the like.

[0138] Specifically, examples of the active ester-based curing agent include dicyclopentadiene-type active ester-based curing agents, naphthalene-type active ester-based curing agents containing a naphthalene structure, active ester-based curing agents containing an acetylated product of phenol novolak, active ester-based curing agents containing a benzoylated product of phenol novolak, active ester-based curing agents that are acetylated products of phenol novolak, and active ester-based curing agents containing a styryl group and a naphthalene structure. Among them, as the active ester-based curing agent, it is preferably one or more curing agents selected from dicyclopentadiene-type active ester-based curing agents and naphthalene-type active ester-based curing agents containing a naphthalene structure, and more preferably a naphthalene-type active ester-based curing agent containing a naphthalene structure.

[0139] Examples of commercially available active ester-based curing agents include, as active ester resins containing a dicyclopentadiene type diphenol structure, "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000-65T", "HPC-8000H-65TM", "HPC-8000L-65TM" manufactured by DIC Corporation; as active ester resins containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "HP-B-8151-62T", "HP-C-8151-62T" manufactured by DIC Corporation; as phosphorus-containing active ester resins, "EXB9401" manufactured by DIC Corporation; as active ester resins that are acetylated products of phenol novolac, "DC808" manufactured by Mitsubishi Chemical Corporation; as active ester resins that are benzoylated products of phenol novolac, "YLH1026", "YLH1030", "YLH1048" manufactured by Mitsubishi Chemical Corporation; and as active ester resins containing a styryl group and a naphthalene structure, "PC1300-02-65MA" manufactured by Air Water Incorporated, etc.

[0140] From the viewpoint of significantly obtaining the effects of the present invention, the active ester group equivalent of the active ester-based curing agent is preferably 50 g / eq. or more, more preferably 100 g / eq., preferably 500 g / eq. or less, more preferably 400 g / eq. or less, and even more preferably 300 g / eq. or less. The active ester group equivalent is the mass of the active ester-based curing agent containing 1 equivalent of the active ester group.

[0141] As phenol-based curing agents and naphthol-based curing agents, those having a novolac structure are preferred from the viewpoints of heat resistance and water resistance. Also, from the viewpoint of adhesion to the conductor layer, nitrogen-containing phenol-based curing agents and nitrogen-containing naphthol-based curing agents are preferred, and phenol-based curing agents and naphthol-based curing agents containing a triazine skeleton are more preferred. From the viewpoint of realizing an insulating layer that is good in all of heat resistance, water resistance, and adhesion to the conductor layer, phenol-based curing agents and naphthol-based curing agents having both a triazine skeleton and a novolac structure are even more preferred.

[0142] Specific examples of phenolic curing agents and naphtholic curing agents include, for example, "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN", "CBN", "GPH-65", "GPH-78", "GPH-103" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC Corporation; "GDP-6115L", "GDP-6115H", "ELPC75", etc. manufactured by Gunei Chemical Industry Co., Ltd.

[0143] The carbodiimide-based curing agent is a compound having one or more carbodiimide groups (-N = C = N-) in one molecule, and the carbodiimide-based curing agent is preferably a compound having two or more carbodiimide groups in one molecule. Specific examples of the carbodiimide-based curing agent include, for example, Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.), V-09 (carbodiimide group equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Inc.; Stabaxol (registered trademark) P (carbodiimide group equivalent: 302 g / eq.) manufactured by LANXESS.

[0144] Examples of the acid anhydride curing agent include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule are preferred. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available products of the acid anhydride curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd., "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200", "HN-5500" manufactured by Resonaak Co., Ltd., and "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Cray Valley Co., Ltd. etc.

[0145] The amine-based curing agent may be a curing agent having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propanediamine, and the like. bis(4-aminophenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. The amine-based curing agent may be a commercially available product, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0146] Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0147] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene)) benzene, bis(4-cyanate phenyl) thioether, and bis(4-cyanate phenyl) ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which part of these cyanate resins is triazine-formed, and the like. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", "BA230S75" (prepolymer in which part or all of bisphenol A dicyanate is triazine-formed and becomes a trimer), etc. manufactured by Lonza.

[0148] Examples of thiol curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanurate, and the like.

[0149] (C) When the epoxy equivalent of the epoxy resin is taken as 1, (D) the active hydrogen equivalent of the curing agent is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 0.7 or more or 0.8 or more, and preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less, 1.8 or less, or 1.6 or less. Here, the "epoxy equivalent of the epoxy resin" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. Also, the "active hydrogen equivalent of the curing agent" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active hydrogen equivalent of the curing agent.

[0150] When the content of the non-volatile components in components (A) to (D) is 100% by mass, the content of the curing agent (D) in the resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 23% by mass or more or 25% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less or 54% by mass or less.

[0151] When the resin composition contains components other than components (A) to (D), the content of the curing agent (D) in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more or 7% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less or 19% by mass or less when the non-volatile components in the resin composition are 100% by mass.

[0152] When the resin composition contains components other than components (A) to (D), the content of the curing agent (D) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 22% by mass or more or 25% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less or 53% by mass or less when the resin components in the resin composition are 100% by mass.

[0153] The mass ratio of the (D) curing agent to the (C) epoxy resin in the resin composition ((content of component (D)) / (content of component (C))) is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 0.7 or more or 0.8 or more, and preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less or 1.7 or less.

[0154] <(E) Inorganic filler> The resin composition may contain, as an optional component, an (E) inorganic filler. The (E) inorganic filler as component (E) may be contained in the resin composition in a particulate state. The (E) inorganic filler may be used alone or in combination of two or more.

[0155] Examples of the material of the (E) inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum silicate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred as the silica. It may be used alone or in combination of two or more.

[0156] (E) Examples of commercially available inorganic fillers include "SP60-05", "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "Cellspheres", "MGH-005" manufactured by Taiheiyo Cement Corporation; "Esferic", "BA-1" manufactured by JGC Catalysts & Chemicals Ltd., etc.

[0157] (E) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, using a laser diffraction / scattering type particle size distribution measuring device, a volume-based particle size distribution of the inorganic filler is created, and the particle size (median diameter, 50% particle size D 50 ) at which the value of the cumulative distribution becomes 50% can be measured as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample can be measured for the volume-based particle size distribution of the inorganic filler using a laser diffraction type particle size distribution measuring device with the light source wavelengths of blue and red, and the average particle size can be calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0158] (E) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By being surface-treated, the moisture resistance and dispersibility of component (E) can be enhanced. Examples of the surface treatment agent include silane coupling agents such as vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, isocyanurate-based silane coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, acid anhydride-based silane coupling agents; non-silane coupling - alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; silazane compounds, etc. The surface treatment agent may be used alone or in combination of two or more kinds.

[0159] Examples of commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[0160] From the viewpoint of improving dispersibility, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, 100% by mass of the (E) inorganic filler is preferably surface-treated with 0.2 to 8% by mass of the surface treatment agent, more preferably surface-treated with 0.2 to 5% by mass of the surface treatment agent, and even more preferably surface-treated with 0.3 to 3% by mass of the surface treatment agent.

[0161] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. (E) The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more, from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and even more preferably 0.5 mg / m 2 or less. The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0162] The content of the (E) inorganic filler in the resin composition is not particularly limited, but when the non-volatile components in the resin composition are 100% by mass, it can be, for example, 0.1% by mass or more, 1% by mass or more, or 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, 40% by mass or more, 50% by mass or more, or 59% by mass or more. The upper limit of the content can be, for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 77% by mass or less, or 75% by mass or less.

[0163] <(F) Curing accelerator> The resin composition may contain, as an optional component, (F) a curing accelerator. The (F) curing accelerator as the component (F) does not include those corresponding to the above-described components (A) to (E). The (F) curing accelerator may be used alone or in combination of two or more kinds.

[0164] Examples of the (F) curing accelerator include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, peroxide-based curing accelerators, and the like. In one embodiment, the (F) curing accelerator preferably contains one or more curing accelerators selected from amine-based curing accelerators and imidazole-based curing accelerators.

[0165] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene, and the like.

[0166] Commercially available products may be used as the amine-based curing accelerator. For example, "DMAP" manufactured by Tokyo Chemical Industry Co., Ltd.; "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc., and the like can be mentioned.

[0167] Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 6-2-(2-methyl-1H-imidazol-1-yl)ethyl-1,3,5-triazine-2,4-diamine, mixtures thereof, and adducts of the imidazole compounds and epoxy resins.

[0168] As the imidazole-based curing accelerator, commercially available products may be used. For example, "1B2PZ", "2MZA-PW", "2PHZ-PW", "C11Z-A", "2MAOK-PW", "2E4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can be mentioned.

[0169] Examples of phosphorus-based curing accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine;Aromatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenylether, etc. are mentioned.;

[0170] Examples of the urea-based curing accelerators include aliphatic dimethylureas such as 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; and aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea].

[0171] Examples of the guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide.

[0172] Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0173] Examples of the peroxide-based hardening accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide. As the peroxide-based hardening accelerator, commercially available products can be used, and for example, "Perk Mill D" manufactured by NOF Corporation can be mentioned.

[0174] The content of the (F) hardening accelerator in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it can be, for example, 0.001% by mass or more, or 0.01% by mass or more, preferably 0.10% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.17% by mass or more. The upper limit of the content can be, for example, 5.0% by mass or less, preferably 1.0% by mass or less, more preferably 0.50% by mass or less, and still more preferably 0.30% by mass or less.

[0175] The content of the (F) curing accelerator in the resin composition is not particularly limited. However, when the resin component in the resin composition is 100% by mass, it can be, for example, 0.01% by mass or more, or 0.10% by mass or more, preferably 0.30% by mass or more, more preferably 0.50% by mass or more, still more preferably 0.55% by mass or more or 0.58% by mass or more. The upper limit of the content can be, for example, 5.0% by mass or less, preferably 3.0% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.90% by mass or less or 0.85% by mass or less.

[0176] <(G) Thermoplastic resin> The resin composition may contain, as an optional component, a (G) thermoplastic resin. The (G) thermoplastic resin as the (G) component does not include those corresponding to the above-mentioned components (A) to (F). The (G) thermoplastic resin may be used alone or in combination of two or more.

[0177] Examples of the (G) thermoplastic resin include phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. In one embodiment, the (G) thermoplastic resin preferably contains a phenoxy resin.

[0178] The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably 8000 or more, more preferably 10000 or more, still more preferably 20000 or more or 30000 or more. The upper limit is preferably 100000 or less, more preferably 70000 or less, still more preferably 60000 or less. The Mw of the thermoplastic resin in terms of polystyrene is measured by the GPC method. Specifically, the Mw of the thermoplastic resin in terms of polystyrene is measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as the measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as the column, and chloroform or the like as the mobile phase at a column temperature of 40°C, and can be calculated using the calibration curve of standard polystyrene.

[0179] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Corporation; "YX8100" (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7800BH40", "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; etc.

[0180] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Lica Coat SN20" and "Lica Coat PN20" manufactured by Nippon Rika Kogyo Co., Ltd., and the like. Specific examples of the polyimide resin also include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetracarboxylic dianhydride (described in JP-A-2006-37083), and modified polyimides such as polyimide containing a polysiloxane skeleton (described in JP-A-2002-12667 and JP-A-2000-319386).

[0181] Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include, for example, the Esrec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; and the like.

[0182] Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0183] Examples of the polybutadiene resin include resins containing a hydrogenated polybutadiene skeleton, hydroxyl group-containing polybutadiene resin, phenolic hydroxyl group-containing polybutadiene resin, carboxy group-containing polybutadiene resin, acid anhydride group-containing polybutadiene resin, epoxy group-containing polybutadiene resin, isocyanate group-containing polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

[0184] Specific examples of the polyamideimide resin include "Vironmax HR11NN" and "Vironmax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimide such as "KS9100" and "KS9300" (polyamideimide containing polysiloxane backbone) manufactured by Hitachi Chemical Co., Ltd.

[0185] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0186] Specific examples of the polysulfone resin include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers, LLC.

[0187] Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE.

[0188] Examples of the polycarbonate resin include hydroxyl group-containing carbonate resin, phenolic hydroxyl group-containing carbonate resin, carboxyl group-containing carbonate resin, acid anhydride group-containing carbonate resin, isocyanate group-containing carbonate resin, urethane group-containing carbonate resin, etc. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, Inc., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., etc. Specific examples of the polyetheretherketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Co., Ltd.

[0189] Examples of the polyester resin include, for example, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethylene terephthalate resin, etc.

[0190] The content of the (G) thermoplastic resin in the resin composition is not particularly limited. However, when the non-volatile components in the resin composition are taken as 100% by mass, it can be, for example, 0.01% by mass or more, or 0.05% by mass or more, preferably 0.10% by mass or more, more preferably 0.15% by mass or more, still more preferably 0.18% by mass or more, or 0.20% by mass or more. The upper limit of the content can be, for example, 5% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.4% by mass.

[0191] The content of the (G) thermoplastic resin in the resin composition is not particularly limited. However, when the resin components in the resin composition are taken as 100% by mass, it can be, for example, 0.01% by mass or more, or 0.10% by mass or more, preferably 0.30% by mass or more, more preferably 0.50% by mass or more, still more preferably 0.60% by mass or more, or 0.70% by mass or more. The upper limit of the content can be, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less.

[0192] <(H) Other additives> In addition to the above-described components, the resin composition may further contain (H) other additives as optional components. Examples of (H) optional additives include radical polymerizable compounds; elastomers; polymerization initiators; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as benton and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photopolymerization initiation aids such as tertiary amines; photosensitizers such as pyralidones, anthracenes, coumarins, xanthones, and thioxanthones. The (H) other additives as component (H) may be used alone or in combination of two or more.

[0193] <(I) Solvent> In addition to the non-volatile components described above, the resin composition may contain, as a volatile component, (I) a solvent. As the (I) solvent, known solvents can be appropriately used, the type thereof is not particularly limited, and it is preferably an organic solvent. Examples of the (I) solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The (I) solvent may be used alone or in combination of two or more in any ratio.

[0194] The resin composition can be produced, for example, by adding components (A), (B), (C), (D), and, if necessary, components (E), (F), (G), (H), and (I) to an arbitrary preparation container in an arbitrary order and / or partially or entirely simultaneously and mixing them. Further, during the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or throughout the process. Further, during or after the process of adding and mixing, the resin composition may be stirred or shaken using a stirring device or a shaking device such as a mixer to be uniformly dispersed. Defoaming may be performed under low-pressure conditions such as under vacuum simultaneously with stirring or shaking.

[0195] [Properties of Resin Composition] The cured product of the resin composition of the present invention exhibits the property of being excellent in elongation characteristics. Therefore, according to the resin composition of the present invention, an insulating layer excellent in mechanical strength is provided. Specifically, the elongation rate (breaking elongation) at 23°C of the cured product obtained by heating the resin composition at 200°C for 90 minutes is preferably 1.3% or more, more preferably 1.5% or more, still more preferably 1.7% or more. The upper limit is not particularly limited, and may be 10% or less, etc. The elongation rate (breaking elongation) can be measured according to the method described in Test Example 1 below.

[0196] The cured product of the resin composition of the present invention exhibits the property of being excellent in adhesion to the plated conductor layer. That is, when a conductor layer is formed by plating on the cured product of the resin composition, high adhesion can be obtained between the conductor layer and the cured product. Therefore, according to the resin composition of the present invention, an insulating layer excellent in plating adhesion is provided. The adhesion strength to plated copper is preferably 0.20 kgf / cm or more, more preferably 0.30 kgf / cm or more, still more preferably 0.40 kgf / cm or more. The upper limit is not particularly limited, and may be 10 kgf / cm or less, etc. The adhesion strength can be measured according to the method described in Test Example 2 below.

[0197] The cured product of the resin composition of the present invention may have the characteristic of low dissipation factor (Df). Therefore, in one embodiment, as in Test Example 3 below, the dissipation factor (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23°C is, for example, less than 0.0040, preferably 0.0035 or less, more preferably 0.0030 or less, still more preferably 0.0025 or less or less than 0.0025. The lower limit is not particularly limited, but may be 0.0001 or more.

[0198] The cured product of the resin composition of the present invention may have the characteristic of low relative permittivity (Dk). Therefore, in one embodiment, as in Test Example 3 below, the relative permittivity (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23°C is, for example, less than 3.5, preferably 3.4 or less, more preferably 3.3 or less, still more preferably 3.2 or less.

[0199] [Use of the resin composition] The resin composition of the present invention can be used for forming an insulating layer, and is particularly preferably used for forming an insulating layer of a circuit board. Further, the resin composition can be used for manufacturing a resin sheet. Usually, an insulating layer is formed using this resin sheet. Further, the resin composition may be used for other uses, for example, it may be used for uses such as solder resist, underfill material, die bonding material, hole filling resin, encapsulating resin, and component embedding resin.

[0200] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed on the support. The resin composition layer contains the above-described resin composition, and preferably contains only the above-described resin composition.

[0201] From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less. The lower limit of the thickness of the resin composition layer can be, for example, 1 μm or more, 3 μm or more, 5 μm or more, etc.

[0202] Examples of the support include films of plastic materials, metal foils, and release papers, with films of plastic materials and metal foils being preferred.

[0203] When using a film of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0204] When using a 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 single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0205] The support may be subjected to surface treatments such as mat treatment, corona treatment, antistatic treatment, etc. on the surface that is joined to the resin composition layer.

[0206] As the support, a support with a release layer having a release layer on the surface that joins with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd-based release agents, polyolefin-based release agents, urethane-based release agents, and silicone-based release agents. Examples of commercially available products of release agents include "SK-1", "AL-5", "AL-7", etc. manufactured by Lintec Corporation, which are alkyd resin-based release agents. Further, examples of commercially available products of supports with release layers include "PET501010", "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of a silicone-based release agent or an alkyd resin-based release agent; "Lumirror T60" manufactured by Toray Industries, Inc.; "Purex" manufactured by Teijin Limited; "Unipile" manufactured by Unitika Ltd., etc.

[0207] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, and preferably 75 μm or less, more preferably 60 μm or less, still more preferably 50 μm or less. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0208] When using a metal foil as the support, a metal foil with a support substrate in which a support substrate that can be peeled from the thin metal foil is laminated may be used. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When using a metal foil with a support substrate as the support, the resin composition layer is provided on the metal foil.

[0209] In the metal foil with a support substrate, the material of the support substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When using a copper foil as the support substrate, it may be an electrolytic copper foil or a rolled copper foil. Further, the release layer is not particularly limited as long as the metal foil can be peeled from the support substrate, and examples thereof include an alloy layer of elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic film, etc.

[0210] In the metal foil with a support substrate, as the material of the metal foil, for example, copper foil or copper alloy foil is preferable.

[0211] In the metal foil with a support substrate, the thickness of the support substrate is not particularly limited, but a range of 10 μm to 150 μm is preferable, and a range of 10 μm to 100 μm is more preferable. Further, the thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0212] The resin sheet may optionally include any member as necessary. For example, the resin sheet may include a protective film that protects the resin composition layer. The protective film is usually provided on the surface that is not joined to the support of the resin composition layer (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. When the protective film is provided, adhesion of dust and scratches to the surface of the resin composition layer can be suppressed.

[0213] The resin sheet can be manufactured, for example, by a method including forming a resin composition layer on a support. Specifically, a liquid (varnish-like) resin composition as it is, or a liquid (varnish-like) resin composition prepared by mixing a solvent and the resin composition is applied onto the support, and further dried as necessary to form a resin composition layer, thereby manufacturing the resin sheet. As the solvent, the same solvents as those described as (I) solvents in the components of the resin composition may be used.

[0214] The application of the resin composition can be performed using a coating device such as a die coater. Further, the drying can be carried out, for example, by a drying method such as heating or hot air blowing. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it may vary depending on the boiling point of the solvent, for example, when a resin composition containing 30% by mass to 60% by mass of the solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0215] The manufactured resin sheet can be wound and stored in a roll. When the resin sheet has a protective film, usually, the resin sheet can be used by peeling off the protective film.

[0216] [Circuit board] The circuit board of the present invention includes a cured product of the above-described resin composition. Usually, the circuit board includes an insulating layer, and this insulating layer includes a cured product of the resin composition. The insulating layer may include only the cured product of the resin composition. The thickness of the insulating layer is not particularly limited and may be, for example, in the same range as the thickness of the resin composition layer provided in the resin sheet.

[0217] Preferably, the circuit board includes an inner layer substrate, and the above-described insulating layer is provided on this inner layer substrate. Further, the circuit board may include a conductor layer. For example, a conductor layer may be provided on the insulating layer. Hereinafter, an example of a preferred method for manufacturing a circuit board will be described.

[0218] The method for manufacturing a circuit board according to a preferred example is Step (I) of forming a resin composition layer on the inner layer substrate, Step (II) of curing the resin composition layer and includes.

[0219] The "inner layer substrate" is a member that serves as a base material of the circuit board, and examples include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Further, the inner layer substrate may have a conductor layer on one or both sides thereof. Further, the conductor layer provided on the inner layer substrate may be pattern-processed. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Further, when manufacturing a circuit board, an intermediate product on which an insulating layer and / or a conductor layer should be further formed is also included in the term "inner layer substrate". Further, an inner layer substrate incorporating components may be used.

[0220] The formation of the resin composition layer on the inner layer substrate can be performed, for example, by laminating a resin sheet and the inner layer substrate. The lamination of the resin sheet and the inner layer substrate is carried out such that the resin composition layer of the resin sheet and the inner layer substrate are joined. This lamination may be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). Note that it is preferable to press through an elastic material such as a heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate instead of directly pressing the thermocompression bonding member against the resin sheet.

[0221] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0222] The lamination may be carried out by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Niko Materials Co., Ltd., a batch type vacuum pressure laminator, and the like.

[0223] The method for manufacturing a circuit board may include, after the lamination, performing a smoothing process on the resin sheet, for example, by pressing the thermocompression bonding member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process may be the same as the thermocompression bonding conditions for the above lamination. The smoothing process can be carried out by a commercially available laminator. The lamination and the smoothing process may be continuously carried out using the above commercially available vacuum laminator.

[0224] The method for manufacturing a circuit board of the present invention includes a step (II) of curing the resin composition layer after the step (I). By curing the resin composition layer in the step (II), an insulating layer can be formed.

[0225] The curing of the resin composition layer is usually performed by thermal curing. The thermal curing conditions of the resin composition layer may vary depending on the type of the resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. Also, the curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0226] The method for manufacturing a circuit board may include preheating the resin composition layer at a temperature lower than the curing temperature before the thermal curing of the resin composition layer. For example, prior to thermally curing the resin composition layer, the resin composition layer is usually preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C for usually 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes. The preheating is usually performed after the step (I). Also, when a smoothing treatment is performed after the lamination of the inner layer substrate and the resin sheet, the preheating may be performed after the smoothing treatment.

[0227] When using a resin sheet, the method for manufacturing a circuit board may include a step of peeling the support of the resin sheet after the lamination of the inner layer substrate and the resin sheet. The peeling of the support may be performed between the step (I) and the step (II), or may be performed after the step (II). Also, when the method for manufacturing a circuit board includes a step (III) of forming holes in the insulating layer, a step (IV) of roughening the insulating layer, and a step (V) of forming a conductor layer as described later, the peeling of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or between the step (IV) and the step (V).

[0228] The method for manufacturing a circuit board may include a step (III) of forming holes such as via holes and through holes in the insulating layer after step (II). The method for forming the holes can be selected according to factors such as the composition of the resin composition used for forming the insulating layer. For example, the holes may be formed by a processing method such as drilling, laser processing, or plasma processing, and among them, laser processing is preferable. For example, after peeling the support, the insulating layer may be irradiated with laser light to form holes, or the insulating layer may be irradiated with laser light through the support to form holes. The dimensions and shape of the holes may be appropriately determined according to the design of the circuit board.

[0229] The method for manufacturing a circuit board may include a step (IV) of performing a roughening treatment on the insulating layer. According to the roughening treatment, roughening of the surface of the insulating layer can be performed. Also, according to the roughening treatment, smears (resin residues) can be removed from the insulating layer. Therefore, this roughening treatment is sometimes called a "desmearing treatment". For example, when holes are formed in step (III), smears may be formed in the holes, so it is preferable to perform the roughening treatment of step (IV) after step (III) to remove the smears.

[0230] The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the circuit board can be adopted. For example, a swelling treatment with a swelling liquid, an oxidation treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid may be sequentially performed on the insulating layer to perform the roughening treatment.

[0231] Examples of the swelling liquid used for the roughening treatment include, for example, an alkaline solution, a surfactant solution, etc., and an alkaline solution is preferable. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include, for example, "Swelling Dip Security P" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid can be carried out, for example, by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0232] Examples of the oxidizing agent used for the roughening treatment include, for example, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Also, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0233] As the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and examples of commercially available products include, for example, "Reduction Solution Security P" manufactured by Atotech Japan Co., Ltd. The neutralization treatment with the neutralizing liquid can be carried out by immersing the treated surface subjected to the oxidation treatment with the oxidizing agent in the neutralizing liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability, a method of immersing the object subjected to the oxidation treatment with the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0234] The method for manufacturing a circuit board may include a step (V) of forming a conductor layer on an insulating layer. When the method for manufacturing a circuit board includes step (III) or (IV), the step (V) of forming a conductor layer is preferably performed after steps (III) and (IV) in general.

[0235] The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is 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 copper is even more preferable.

[0236] The conductor layer may have a single-layer structure, or may have a multi-layer structure including two or more single metal layers or alloy layers made of different types of metals or alloys. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0237] The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, and more preferably 5 μm to 30 μm.

[0238] The conductor layer may be formed by plating. For example, a plating layer (plating seed layer) can be formed on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. From the viewpoint of manufacturing simplicity, the semi-additive method is preferred. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0239] First, an electroless plating layer (plating seed layer) is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed electroless plating layer to expose a part of the electroless plating layer corresponding to the desired wiring pattern. After forming an electrolytic plating layer by electrolytic plating on the exposed electroless plating layer, the mask pattern is removed. Thereafter, the unnecessary electroless plating layer can be removed by etching to form a conductor layer having a desired wiring pattern.

[0240] As another example, the conductor layer may be formed using a metal foil. When forming the conductor layer using a 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 surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a known technique such as a subtractive method or a modified semi-additive method. The metal foil can be manufactured by a known method such as an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Metals, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., etc.

[0241] When a conductor layer is formed on an insulating layer, the method for manufacturing a circuit board may include performing an annealing process after the formation of the conductor layer. According to the annealing process, the adhesion between the insulating layer and the conductor layer can be enhanced. The annealing process can be performed, for example, by heating at 150°C to 210°C for 20 minutes to 180 minutes.

[0242] In the method for manufacturing a circuit board, each of the above-described steps may be performed only once, or may be repeated two or more times. For example, steps (I) to (V) may be repeatedly performed to form a circuit board having a multilayer structure such as a multilayer printed wiring board including a plurality of insulating layers and conductor layers.

[0243] The method for manufacturing a circuit board may further include any arbitrary steps in combination with the above-described steps. For example, the method for manufacturing a circuit board may include a step of providing a semiconductor chip so as to be joined to the conductor layer. As a specific example, when manufacturing a circuit board for a semiconductor chip package including a semiconductor chip, the method for manufacturing a circuit board may include a step of providing a semiconductor chip. The semiconductor chip can adopt appropriate conditions under which the terminal electrodes of the semiconductor chip and the conductor layer formed on the insulating layer can be conductively connected. For example, the conditions used in flip chip mounting can be adopted. Also, the semiconductor chip may be joined via an insulating adhesive, or may be joined by reflow. Further, if necessary, the provided semiconductor chip may be filled with a mold underfill material. Also, the method for manufacturing a circuit board may include, for example, a step of forming a sealing layer, a step of forming a solder resist layer, a step of dicing the manufactured circuit board into individual pieces, and the like.

[0244] Examples of the circuit board include, for example, a printed wiring board and a semiconductor chip package. Examples of the semiconductor chip package include, for example, FC-CSP, MIS-BGA package, ETS-BGA package, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP. In these semiconductor chip packages, it is preferable to form a redistribution layer formation layer with an insulating layer obtained by curing the above-described resin composition layer. However, the circuit board is not limited to those exemplified here.

[0245] [Semiconductor device] The above-described circuit board can be used in the manufacture of a semiconductor device. The semiconductor device includes the above-described circuit board. Examples of the semiconductor device include various semiconductor devices used in electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, and airplanes, etc.).

Example

[0246] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "mass%", respectively, unless otherwise specified. The temperature conditions when there is no particular temperature designation are under room temperature (23°C), and the pressure conditions when there is no particular pressure designation are under atmospheric pressure (1 atm).

[0247] <Synthesis Example 1: Synthesis of styrene divinylbenzene polymer compound A> A 300 mL separable flask equipped with a nitrogen inlet tube and a stirrer was prepared. 50 mL of toluene, 50 mL of styrene, 5 mL of divinylbenzene, 25.0 g of diphenyldisulfide, 100 mg of benzoyl peroxide, and 0.25 mL of N,N-dimethylaniline were added to this flask, and the mixture was stirred at 30 °C for 760 hours under a nitrogen stream to carry out the reaction. The reaction product was poured into about 400 mL of methanol containing tert-butylhydroquinone, and the precipitate was collected and dried under reduced pressure. The number of residual vinyl groups (pendent vinyl groups) in the obtained styrene-divinylbenzene polymer was 4.0 per polymer molecule. The weight average molecular weight of the above styrene-divinylbenzene polymer was 28,300, and it was soluble in common solvents such as toluene and acetone.

[0248] <Synthesis Example 2: Synthesis of maleimide compound B> Maleimide compound B was synthesized by the method described in Synthesis Example 1 of JP-A-2020-500211 of the Japan Institute of Invention and Innovation, and a MEK solution (non-volatile component: 70% by mass) of the maleimide compound B was obtained.

[0249] <Example 1> 10 parts of a polystyrene resin having an acryloyl group in the side chain (Mitsui Chemicals, Inc.'s "XPA-8255", n-butyl acetate solution with a non-volatile component of 70% by mass, molecular weight 5,000), 10 parts of a maleimide resin containing an aliphatic skeleton (Shin-Etsu Chemical Co., Ltd.'s "SLK-6895-T90", toluene solution with a non-volatile component of 90% by mass), 10 parts of a biphenyl-type epoxy resin (Nippon Kayaku Co., Ltd.'s "NC-3000-L", epoxy equivalent 269 g / eq.), 5 parts of a bixylenol-type epoxy resin (Mitsubishi Chemical Corporation's "YX-4000HK", epoxy equivalent 194 g / eq.), 5 parts of a bisphenol-type epoxy resin (Nippon Steel Chemical & Material Co., Ltd.'s "ZX-1059", a 1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent 169 g / eq.), 40 parts of an active ester-based curing agent (DIC Corporation's "HP-B-8151-62T", toluene solution with a non-volatile component of 62% by mass, active group equivalent 238 g / eq.), 8 parts of a phenolic curing agent (DIC Corporation's "LA3018-50P", 1-methoxy-2-propanol solution with a non-volatile content of 50% by mass, phenol equivalent 151 g / eq.), 6 parts of a carbodiimide-based curing agent (Nippon Kayaku Co., Ltd.'s "V-03", toluene solution with a non-volatile content of 50% by mass, functional group equivalent 231 g / eq.), spherical silica (Admatechs Co., Ltd.'s "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m 2 / g) surface-treated with an amine-based silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM-573") 180 parts, 0.5 part of an amine-based curing accelerator (Tokyo Chemical Industry Co., Ltd.'s "DMAP"), and to a phenoxy resin (Mitsubishi Chemical Corporation's "YX7553BH30", 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass), 10 parts of MEK and 10 parts of cyclohexanone were further added and uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish.

[0250] <Examples 2 to 12, Comparative Examples 1 to 7> A resin varnish was prepared in the same manner as in Example 1, except that the components were mixed with the composition shown in Table 1. In Table 1, the meanings of the abbreviations are as follows.

[0251] (A) A polystyrene resin having a radically polymerizable group in the side chain and a molecular weight of less than 50,000 · "XPA-8255": A polystyrene resin manufactured by Mitsui Chemicals, Inc., having an acryloyl group in the side chain, an n-butyl acetate solution with a non-volatile component of 70% by mass, styrene-based monomer unit / acrylic acid ester-based monomer unit (mol) = 13.2, and a molecular weight of 5,000 · "XPA-8272": A polystyrene resin manufactured by Mitsui Chemicals, Inc., having an acryloyl group in the side chain, an n-butyl acetate solution with a non-volatile component of 60% by mass, styrene-based monomer unit / acrylic acid ester-based monomer unit (mol) = 10.2, and a molecular weight of 5,000 · "Compound A": A styrene divinylbenzene polymer compound A obtained in Synthesis Example 1, with a weight average molecular weight of 28,300 · "ODV-XET-X04": A polystyrene resin manufactured by Nippon Steel Chemical & Material Co., Ltd., having a vinylphenyl group in the side chain, a toluene solution with a non-volatile component of 50% by mass, and a weight average molecular weight of 31,100

[0252] (A’-1) A polystyrene resin having a reactive functional group other than a radically polymerizable group in the side chain · "RPS-1005": "Epocros (registered trademark) RPS-1005" manufactured by Nippon Shokubai Co., Ltd., a polystyrene resin having an oxazoline group in the side chain, and an oxazoline group equivalent of approximately 3,700 g / eq.

[0253] (A’-2) A polystyrene resin having a radically polymerizable group and a molecular weight of 50,000 or more · "CS-700": A polystyrene resin manufactured by Nippon Kayaku Co., Ltd., having a vinyl group in the side chain, and a molecular weight of 150,000

[0254] (A’-3) Polystyrene having a radically polymerizable functional group at the molecular terminal · "OPE-2st": Vinylbenzyl-modified polyphenylene ether manufactured by Mitsubishi Gas Chemical Company, Inc., a toluene solution with a non-volatile component of 65% by mass

[0255] (A’-4) A polystyrene resin having no reactive functional group · "G-100C": Manufactured by Toyo Styrene Co., polystyrene resin, weight average molecular weight 402,000

[0256] (B) Maleimide resin · "SLK-6895-T90": Manufactured by Shin-Etsu Chemical Co., maleimide compound having a carbon skeleton derived from dimer acid, toluene solution with a non-volatile component of 90 mass% · "MIR-5000-60T": Manufactured by Nippon Kayaku Co., maleimide compound having a biphenyl skeleton, maleimide group equivalent 266 g / eq. · "BMI-1500": Manufactured by Designer Molecules Inc., maleimide compound having a carbon skeleton derived from dimer acid · "Compound B": Maleimide compound B obtained in Synthesis Example 2

[0257] (C) Epoxy resin · "NC-3000-L": Manufactured by Nippon Kayaku Co., biphenyl type epoxy resin, epoxy equivalent 269 g / eq. · "YX-4000HK": Manufactured by Mitsubishi Chemical Corporation, bixylenol type epoxy resin, epoxy equivalent 194 g / eq. · "ZX-1059": Manufactured by Nippon Steel Chemical & Material Co., a 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent 169 g / eq.

[0258] (D) Curing agent · "HP-B-8151-62T": Manufactured by DIC Corporation, active ester type curing agent having a naphthalene structure, active ester group equivalent 238 g / eq. · "LA3018-50P": Manufactured by DIC Corporation, phenolic curing agent having a triazine skeleton and a cresol novolak structure, 1-methoxy-2-propanol solution with a non-volatile component of 50 mass%, hydroxyl group equivalent 151 g / eq. · "GPH-103": Manufactured by Nippon Kayaku Co., biphenyl aralkyl type phenolic curing agent, hydroxyl group equivalent 231 g / eq. · "V-03": Manufactured by Nisshinbo Chemical Inc., carbodiimide type curing agent, toluene solution with a non-volatile component of 50 mass%, carbodiimide group equivalent 216 g / eq.

[0259] (E) Inorganic filler · "SO-C2": Spherical silica (manufactured by Admatechs "SO-C2") surface-treated with an amine-based alkoxysilane compound (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573"), average particle size 0.5 μm, specific surface area 5.8 m 2 / g · "UFP-30": Spherical silica (manufactured by Denka "UFP-30") surface-treated with an amine-based alkoxysilane compound (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573"), average particle size 0.3 μm, specific surface area 30.7 m 2 / g

[0260] (F) Curing accelerator · "DMAP": Manufactured by Tokyo Chemical Industry Co., Ltd., amine-based curing accelerator · "C11Z-A": Manufactured by Shikoku Chemicals Corporation, imidazole-based curing accelerator

[0261] (G) Thermoplastic resin · "YX7553BH30": Manufactured by Mitsubishi Chemical Corporation, phenoxy resin, a solution of MEK:cyclohexanone = 1:1 with a non-volatile component of 30% by mass

[0262]

Table 1

[0263] ><Production of resin sheet A> On a PET film (manufactured by Lintec "AL-5", thickness 38 μm), the resin varnishes obtained in the examples and comparative examples were uniformly applied using a die coater so that the thickness of the resin composition layer after drying would be 40 μm. The applied resin varnish was dried at 90°C to 100°C (average 95°C) for 3 minutes to obtain a resin sheet A made of a resin composition.

[0264] ><Test Example 1: Measurement of elongation at break> The resin sheet A produced in the examples and comparative examples was heated at 200 °C for 90 minutes to thermoset the resin composition layer, and then the support was peeled off. The obtained cured product was subjected to a tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd., and the elongation rate (elongation at break) at the time of breakage at 23 °C was measured. The measurement was carried out in accordance with JIS K7127. The measurement was performed 5 times, and the average value of the top 3 points was calculated, and the elongation characteristics were evaluated according to the following evaluation criteria. ○: Elongation at break is 1.7% or more △: Elongation at break is 1.3% or more and less than 1.7% ×: Elongation at break is less than 1.3%

[0265] <Test Example 2: Measurement of Peel Strength of Plated Conductor Layer> (1) Substrate Treatment of Inner Layer Substrate Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (manufactured by Panasonic "R1515A", copper foil thickness 18 μm, substrate thickness 0.8 mm) on which an inner layer circuit was formed were etched with 1 μm using "CZ8101" manufactured by Meck Co., Ltd. to roughen the copper surface. Further, heat treatment was performed in an oven at 130 °C for 30 minutes. Thereby, an inner layer substrate was obtained.

[0266] (2) Lamination of Resin Sheet The resin sheet A produced above was laminated on both sides of the inner layer substrate using a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nichco Materials Co., Ltd.) so that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by reducing the pressure for 30 seconds to make the atmospheric pressure 13 hPa or less, and then pressure-bonding at 100 °C and a pressure of 0.74 MPa for 30 seconds. Subsequently, hot pressing was performed at 100 °C and a pressure of 0.5 MPa for 60 seconds.

[0267] (3) Curing of Resin Composition Layer The resin sheet laminated on the inner layer substrate was heated under curing conditions of 100 °C for 30 minutes and further 180 °C for 30 minutes to thermoset the resin composition layer. An insulating layer was formed by the thermosetting of the resin composition layer. Thereafter, the support was peeled off to obtain a substrate A having a layer structure of insulating layer / inner layer substrate / insulating layer.

[0268] (4) Roughening treatment The above-mentioned substrate A was immersed in a swelling liquid (Attaque Japan Co., Ltd.'s "Swelling Dip·Security Gant P" containing diethylene glycol monobutyl ether) at 60°C for 10 minutes. Next, the sample substrate was immersed in a roughening liquid (Attaque Japan Co., Ltd.'s "Concentrate·Compact P", an aqueous solution of KMnO4: 60 g / L and NaOH: 40 g / L) at 80°C for 20 minutes. Next, the sample substrate was immersed in a neutralizing liquid (Attaque Japan Co., Ltd.'s "Reduction Solution·Security Gant P") at 40°C for 5 minutes. Then, the sample substrate was dried at 80°C for 30 minutes to obtain a roughened substrate B.

[0269] (5) Formation of the conductor layer After the roughened substrate B was immersed in a electroless plating solution containing PdCl2 at 40°C for 5 minutes, it was immersed in an electroless copper plating solution at 25°C for 20 minutes. Then, an annealing treatment was performed on the roughened substrate by heating at 150°C for 30 minutes, and then an etching resist was formed, and pattern formation by etching was performed. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm on the surface of the insulating layer. Next, an annealing treatment was performed by heating at 180°C for 30 minutes to obtain an evaluation substrate C having a conductor layer on the insulating layer.

[0270] (6) Evaluation of adhesion to the plated conductor layer The measurement of the peel strength between the insulating layer and the plated conductor layer was carried out in accordance with Japanese Industrial Standard (JIS C6481). Specifically, the evaluation substrate C obtained above was cut into small pieces with a width of 30 mm and a length of 100 mm. A cut was made in the conductor layer of the obtained small piece using a cutter to surround a rectangular portion with a width of 10 mm. One end of this rectangular portion was peeled off and grasped with a gripping tool (the auto-comb type tester "AC-50C-SL" manufactured by T.S.E. Co., Ltd.), and the load (kgf / cm) when it was peeled off vertically by 35 mm at a speed of 50 mm / min in room temperature (normal temperature) was measured to obtain the peel strength (plating peel strength). The plating adhesion was evaluated according to the following evaluation criteria. ○: The measured value of the load is 0.40 kgf / cm or more △: The measured value of the load is greater than 0.20 kgf / cm and less than 0.40 kgf / cm ×: The measured value of the load is 0.20 kgf / cm or less

[0271] <Test Example 3: Measurement of Dielectric Dissipation Factor (Df) and Relative Dielectric Constant (Dk)> After heating the resin sheet A prepared in the examples and comparative examples at 200 °C for 90 minutes to thermoset the resin composition layer, the support was peeled off. The obtained cured product was cut into test pieces with a width of 2 mm and a length of 80 mm. For the test pieces, using "HP8362B" manufactured by Agilent Technologies, the dielectric dissipation factor (Df) and relative dielectric constant (Dk) were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method. Measurements were performed on three test pieces, and the average value was calculated. The dielectric dissipation factor (Df) and relative dielectric constant (Dk) were evaluated according to the following evaluation criteria. - Evaluation Criteria for Dielectric Dissipation Factor (Df)- ○: The measured value of the dielectric dissipation factor is less than 0.0025 △: The measured value of the dielectric dissipation factor is 0.0025 or more and less than 0.0040 ×: The measured value of the dielectric dissipation factor is 0.0040 or more - Evaluation Criteria for Relative Dielectric Constant (Dk)- ○: The measured value of the relative dielectric constant is less than 3.5 ×: The measured value of the relative dielectric constant is 3.5 or more

[0272] The evaluation results of each example and comparative example are summarized in Table 2 below.

[0273]

Table 2

Claims

1. A resin composition comprising: (A) a polystyrene resin having a radically polymerizable group in the side chain and a molecular weight of less than 50,000; (B) a maleimide resin (excluding those corresponding to component (A)); (C) an epoxy resin; and (D) a curing agent.

2. The resin composition according to claim 1, wherein component (A) has a radically polymerizable group selected from a (meth)acryloyl group and a vinylbenzyl group in the side chain.

3. The resin composition according to claim 1, wherein component (A) has: (a1) a styrene unit which may have a substituent (excluding a radically polymerizable group) on the benzene ring; and (a2) a styrene unit having a radically polymerizable group on the benzene ring and / or (a3) a vinyl unit having a radically polymerizable group (excluding the (a2) unit).

4. The resin composition according to claim 3, wherein the amount of the styrene unit (a1) which may have a substituent (excluding a radically polymerizable group) on the benzene ring is 70% by mass or more based on 100% by mass of component (A).

5. The resin composition according to claim 1, wherein component (A) has a structural unit represented by the following formula (A1) and further has a structural unit represented by the following formula (A2) and / or the following formula (A3). 【Chemical 1】 (In formulas (A1) to (A3), R １ and R 3 each independently represents a substituent (excluding a radically polymerizable group); R ２ and R ４ each independently represents a radically polymerizable group; L represents a divalent linking group (excluding a phenylene group); x, y, and z represent integers of 1 or more; m1 represents 0 or an integer of 1 to 5; m2 represents an integer of 1 to 5; m3 represents 0 or an integer of 1 to 4 and is an integer satisfying the relationship 1 ≦ m2 + m3 ≦ 5.)

6. The resin composition according to claim 1, wherein component (B) has one or more skeletons selected from a carbon skeleton derived from dimer acid, a biphenyl skeleton, and an indane skeleton.

7. The resin composition according to claim 1, wherein component (D) contains one or more curing agents selected from an active ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, and a carbodiimide-based curing agent.

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

9. The resin composition according to claim 1, wherein the total amount of components (A) and (B) is 5% by mass or more and 50% by mass or less when the resin components in the resin composition are 100% by mass.

10. The resin composition according to claim 1, which is used for forming an insulating layer of a circuit board.

11. A cured product of the resin composition according to any one of claims 1 to 10.

12. It includes a support and a resin composition layer formed on the support. A resin sheet in which the resin composition layer contains the resin composition according to any one of claims 1 to 10.

13. A circuit board including a cured product of the resin composition according to any one of claims 1 to 10.

14. A semiconductor device including the circuit board according to claim 13.

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