TW202208475A - resin composition - Google Patents

Abstract

Provided is a resin composition with which it is possible to obtain a cured product having a low relative dielectric constant (Dk) and a low dielectric loss tangent (Df) and having excellent peel strength of a plated conductor layer. The resin composition containing (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a maleimide compound not having an aliphatic chain having 7 or more carbon atoms.

Description

resin composition

The present invention relates to a resin composition containing maleimide. In addition, it relates to a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

As a manufacturing technique of a printed wiring board, the manufacturing method of the build-up method by alternately stacking an insulating layer and a conductor layer is known, for example. In the manufacturing method of the build-up method, generally, the insulating layer is formed by curing the resin composition. In recent years, it is required to further improve the dielectric properties such as the dielectric constant and the dielectric tangent of the insulating layer, and the peel strength of the electroplated conductor layer.

Various maleimide compounds have been known so far (Patent Documents 1 to 3). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2019-203122 [Patent Document 2] International Publication No. 2018/212116 [Patent Document 3] International Publication No. 2020/045489

[The problem to be solved by the invention]

The subject of this invention is to provide the resin composition which can obtain the hardened|cured material which is low in specific capacitance (Dk) and dielectric tangent (Df), and is excellent in the peeling strength of a plated conductor layer. [means to solve the problem]

In order to achieve the subject of the present invention, as a result of careful examination by the present inventors, by using (A) an amine compound having a biphenyl skeleton and (B) maleimide having an aliphatic chain having 7 or more carbon atoms A compound, and (C) a resin composition of a maleimide compound having no aliphatic chain having a carbon number of 7 or more, unexpectedly found that a specific capacitance (Dk) and a low dielectric tangent (Df) can be obtained, and A hardened product having excellent peel strength of a plated conductor layer has completed the present invention.

That is, the present invention includes the following contents. [1] A resin composition comprising (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) A maleimide compound which does not have an aliphatic chain having 7 or more carbon atoms. [2] The resin composition according to the above [1], wherein the component (B) has a maleimide group directly bonded to a carbon atom not constituting an aromatic ring. [3] The resin composition according to the above [1] or [2], wherein the component (C) has a maleimide group directly bonded to a carbon atom constituting an aromatic ring. [4] The resin composition according to any one of the above [1] to [3], wherein the component (A) has a primary amine group. [5] The resin composition according to any one of the above [1] to [4], wherein the component (A) has an amine group directly bonded to a carbon atom constituting an aromatic ring. [6] The resin composition according to any one of the above [1] to [5], wherein the component (A) contains the formula (A1):

[wherein, V and W each independently represent -C(R') ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO-, R Each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent, and h, i and j each independently represent an integer of 0 to 2] The amine compound represented by the repeating unit. [7] The resin composition according to any one of the above [1] to [6], wherein the content of the component (A) is 3 to 40 mass % when the nonvolatile content in the resin composition is 100 mass % %. [8] The resin composition according to any one of the above [1] to [7], wherein the content of the (B) component is 3 to 40 mass % when the non-volatile content in the resin composition is 100 mass % %. [9] The resin composition according to any one of the above [1] to [8], wherein the content of the component (C) is 3 to 40 mass % when the non-volatile content in the resin composition is 100 mass % %. [10] The resin composition according to any one of the above [1] to [9], wherein the mass ratio of (C) component to (B) component ((C) component/(B) component) is 0.5 to 20 . [11] The resin composition according to any one of the above [1] to [10], wherein the mass ratio of (A) component to the total of (B) component and (C) component ((A) component/(B) ) component and (C) component total) is 0.1-0.5. [12] The resin composition according to any one of the above [1] to [11], which further contains (D) a radically polymerizable compound other than the (B) component and the (C) component. [13] The resin composition according to any one of the above [1] to [12], further comprising (E) an inorganic filler. [14] The resin composition according to the above [13], wherein the content of the component (E) is 25% by mass or more when the nonvolatile content in the resin composition is 100% by mass. [15] The resin composition according to any one of the above [1] to [14], wherein the dielectric tangent of the cured product of the resin composition is 0.004 or less when measured at 5.8 GHz and 23°C. [16] The resin composition according to any one of the above [1] to [15], wherein the specific capacitance of the cured product of the resin composition is 2.9 or less when measured at 5.8 GHz and 23°C. [17] A cured product, which is a cured product of the resin composition according to any one of the above [1] to [16]. [18] A sheet-like laminate comprising the resin composition according to any one of the above [1] to [16]. [19] A resin sheet comprising a support, and a resin composition layer formed of the resin composition of any one of the above [1] to [16] provided on the support. [20] A printed wiring board including an insulating layer composed of a cured product of the resin composition according to any one of the above [1] to [16]. [21] A semiconductor device comprising the printed wiring board of the above [20]. [Inventive effect]

According to the resin composition of the present invention, a cured product having low specific capacitance (Dk) and dielectric tangent (Df) and excellent peel strength of the electroplated conductor layer can be obtained. [Form of implementing the invention]

Hereinafter, the present invention will be described in detail based on preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with arbitrary modifications within the scope of the claims and equivalents of the present invention.

<Resin composition> The resin composition of the present invention comprises (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a Maleimide compounds with aliphatic chains above 7. By using such a resin composition, a cured product having low specific capacitance (Dk) and dielectric tangent (Df) and excellent peel strength of the plated conductor layer can be obtained.

The resin composition of the present invention does not have (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) no amine compound having 7 carbon atoms. In addition to the maleimide compound of the aliphatic chain described above, optional components may be further contained. Examples of the arbitrary components include (D) arbitrary radically polymerizable compounds, (E) inorganic fillers, (F) curing accelerators, (G) other additives, and (H) organic solvents. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Amine compound having biphenyl skeleton> The resin composition of the present invention contains (A) an amine compound having a biphenyl skeleton. (A) A component may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types. In one embodiment, the amine group contained in the (A) component can undergo an addition reaction with the (B) component, the (C) component (and when the (D) component is included, the (D) component) or the like. In one embodiment, the component (A) preferably has two or more amino groups in one molecule, and more preferably has three or more amino groups. The component (A) may have any one of a primary amino group, a secondary amino group, and a tertiary amino group as an amino group, and in one embodiment, it is preferable to have a primary amino group. In one embodiment, the component (A) preferably has an amine group (aromatic amine group) directly bonded to a carbon atom constituting an aromatic ring as the amine group, more preferably has a primary aromatic amine group, particularly preferably The amine group contained in the component (A) is only a primary aromatic amine group.

In one embodiment, component (A) preferably contains formula (A1):

[wherein, V and W each independently represent -C(R') ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO- (comparatively Preferably -C(R') ₂ -), R each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom), and h, i and j each independently represent an integer of 0 to 2 (preferably 0)] is an amine compound represented by a repeat unit. In addition, the units of the h unit, the i unit, and the j unit may be the same or different.

In the present specification, the substituent is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an aryl group, an alkyl-aryl group (an aryl group substituted by one or more alkyl groups), an aryl-aryl group (a group substituted by 1 or more Aryl substituted with more than one aryl group), aryl-alkyl (alkyl substituted with more than one aryl group), alkyl-oxy, alkenyl-oxy, aryl-oxy, alkyl -carbonyl, alkenyl-carbonyl, aryl-carbonyl, alkyl-oxy-carbonyl, alkenyl-oxy-carbonyl, aryl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl-carbonyl- When a monovalent substituent such as an oxy group and an aryl-carbonyl-oxy group may be substituted, a divalent substituent such as a pendant oxy group (=O) may be included.

Alkyl (group) refers to a linear, branched and/or cyclic monovalent saturated hydrocarbon group. The alkyl group (group) is not particularly limited, but is preferably an alkyl group having 1 to 14 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 6 or 4 to 10 carbon atoms. Examples of the alkyl (group) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl cyclohexyl, decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl and the like. Alkenyl (group) refers to a linear, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group (group) is not particularly limited, but is preferably an alkenyl group having 2 to 14 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably an alkenyl group having 2 to 6 or 4 to 10 carbon atoms. As an alkenyl group (group), a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a cyclohexenyl group, etc. are mentioned, for example. An aryl group (group) means a monovalent aromatic hydrocarbon group. The aryl group (group) is preferably an aryl group (group) having 6 to 14 carbon atoms. As an aryl group (group), a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc. are mentioned, for example.

The weight average molecular weight (Mw) of the component (A) is preferably 300-4000, more preferably 300-3000, still more preferably 300-2000. The weight average molecular weight of the component (A) can be measured in terms of polystyrene by a gel permeation chromatography (GPC) method.

The functional group equivalent of the amine group of the component (A) is preferably 100 g/eq. to 1000 g/eq., more preferably 100 g/eq. to 500 g/eq. The functional group equivalent of the amine group of the component (A) is the mass of the component (A) per 1 equivalent of the amine group.

A specific example of the component (A) includes, for example, the formula (A2):

The amine compound represented by the repeating unit.

As a commercial item of (A) component, "BAN" (the amine compound of the said formula (A2)) by Nippon Kayaku Co., Ltd., etc. are mentioned, for example.

The content of the (A) component in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40 mass % or less, more preferably 30 mass % or less, and particularly preferably 25 mass % or less. The lower limit of the content of the component (A) in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, and More preferably, it is 3 mass % or more, still more preferably 5 mass % or more, and particularly preferably 7 mass % or more.

<(B) Maleimide compound having an aliphatic chain having 7 or more carbon atoms> The resin composition of the present invention contains (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms. (B) A component may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types. The maleimide compound refers to at least one (preferably two or more) maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1) in one molecule. -based) organic compounds. In one embodiment, the (B) component preferably has a maleimide group directly bonded to a carbon atom that does not constitute an aromatic ring, and the maleimide group contained in the (B) component is particularly preferably Only the maleimide group directly bonded to the carbon atom that does not constitute the aromatic ring.

The aliphatic chain refers to an aliphatic chain in which skeleton atoms are connected via a single bond, a double bond or a triple bond, preferably an aliphatic chain in which the skeleton atoms are connected via a single bond or a double bond, and particularly preferably an aliphatic chain in which the skeleton atoms are connected only via a single bond. In addition, the aliphatic chain may have a branch, but does not constitute a part or all of the ring structure.

The aliphatic chain may be an aliphatic carbon chain with only carbon atoms as backbone atoms (eg, alkylene chain, alkenylene chain, etc.), and in addition to carbon atoms, may also be heteroatoms selected from oxygen atoms, nitrogen atoms and sulfur atoms The heteroatom-containing aliphatic chain (eg, polyalkylene oxide chain, polyalkyleneimine chain, etc.) as the skeleton atom is preferably an aliphatic carbon chain having only carbon atoms as the skeleton atom in one embodiment. The upper limit of the number of carbon atoms in the skeleton atoms of the aliphatic chain is not particularly limited, and may be, for example, 3000 or less, 1000 or less, 100 or less, 50 or less, and the like. The aliphatic chain having 7 or more carbon atoms, preferably the main chain of the aliphatic chain, has 7 or more carbon atoms.

In one embodiment, the maleimide compound of component (B) preferably comprises formula (B1):

[In the formula, A ¹ each independently represents a divalent organic group having an aliphatic chain having 7 or more carbon atoms, A ² each independently represents a divalent organic group that does not have an aliphatic chain having a carbon number of 7 or more, and each B ¹ independently represent a tetravalent organic group having an aromatic ring and/or a non-aromatic ring, n1 and n2 represent an integer of 0 or more (preferably 0 or an integer from 1 to 100), m1 and m2 represent either 1, Others are 0, and the sum of n1 and m1 is 1 or more. The maleimide compound represented by]. In addition, the order of the n1 unit and the n2 unit and the arrangement of each are arbitrary, and include alternating copolymers, block copolymers, random copolymers, and the like. In addition, each unit of n1 unit and n2 unit may be the same or different.

The aromatic ring refers to a ring according to Hückel's rule that the number of electrons contained in the π electron system on the ring is 4n+2 (n is a natural number). The aromatic ring may also be a carbocyclic ring with carbon atoms as ring constituent atoms, or a heterocyclic ring with heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc., as ring constituent atoms, in addition to carbon atoms. Preferably it is a carbocyclic ring. Aromatic rings are not only monocyclic aromatic rings and condensed rings in which two or more monocyclic aromatic rings are condensed, but also include one or more monocyclic non-aromatic rings on one or more monocyclic aromatic rings A condensed ring that undergoes condensation. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an indane ring, a perylene ring, a tetrahydronaphthalene ring, and the like.

A non-aromatic ring means a ring other than an aromatic ring. The non-aromatic ring may be a carbocyclic ring or a heterocyclic ring, and in one embodiment, a carbocyclic ring is preferred. The non-aromatic ring may be a saturated ring or an unsaturated ring, and in one embodiment, a saturated ring is preferable. The non-aromatic ring includes a condensed non-aromatic ring obtained by condensing two or more monocyclic non-aromatic rings such as a cycloalkane ring and a cycloalkene ring, and a monocyclic non-aromatic ring such as a cross-linked hydrocarbon ring. The cycloalkane ring is a monocyclic aliphatic saturated hydrocarbon ring, for example, a ring having 3 to 8 carbon atoms such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring. alkane ring. The cycloolefin ring is a monocyclic aliphatic unsaturated hydrocarbon ring having at least one carbon-carbon double bond, for example, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring. A cycloalkene ring having 4 to 8 carbon atoms such as a ring, a cyclopentadiene ring, and a cyclohexadiene ring. The cross-linked hydrocarbon ring is a non-aromatic ring composed of two or more rings having two or more atoms in total, for example, a norbornane ring, a decahydronaphthalene ring, an adamantane ring, and a tetrahydrodicyclopentadiene ring. Equivalent cross-linked hydrocarbon rings with 8 to 15 carbon atoms.

When n1 is 1 or more, the ratio of n1 to n2 (n2/n1) is preferably 5.0 or less, more preferably 2.0 or less, still more preferably 1.5 or less, and particularly preferably 1.2 or less.

A ¹ each independently represents a divalent organic group having an aliphatic chain having 7 or more carbon atoms. The skeleton atom of the "divalent organic group" represented by A ¹ is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. The following etc.

In one embodiment, each of A ¹ is preferably a divalent group obtained by removing two amine groups from dimer diamine. The dimer diamine refers to a compound in which two terminal carboxyl groups (—COOH) of the dimer acid are substituted with an amino group or an aminomethyl group, and has an aliphatic carbon chain having 7 or more carbon atoms. Dimeric acid, for example, dimer of unsaturated fatty acid (preferably unsaturated fatty acid having 11 to 22 carbon atoms, particularly preferably unsaturated fatty acid having 18 carbon atoms such as oleic acid and linoleic acid) or its hydrogenated product.

In other embodiments, A ¹ is each independently preferably a divalent non-aromatic hydrocarbon group having an aliphatic carbon chain having 7 or more carbon atoms, more preferably the formula (b1):

[In the formula, Y ¹ each independently represents a straight-chain or branched (preferably straight-chain) alkylene group whose number of atoms (preferably the number of atoms in the main chain of the alkylene group) is 7 or more, or the number of atoms (preferably a straight chain) Preferably, the number of atoms in the main chain of the alkenylene group is 7 or more linear or branched (preferably linear) alkenylene (preferably, the number of carbon atoms is 7 or more linear or branched (preferably linear). is a straight chain) alkylidene), ring Z ^y1 represents a cycloalkane ring which may have a group selected from alkyl and alkenyl, or a cycloalkenyl ring (preferably a cycloalkenyl ring which may have a group selected from alkyl and alkenyl) is a cyclohexane ring which may have an alkyl group); d represents 0 or 1 (preferably 1); * represents a bonding site] represents a divalent group.

Alkylene refers to a divalent saturated hydrocarbon group, the number of carbon atoms of a straight-chain or branched alkyl group with a carbon number of 7 or more, such as 7-200, preferably 7-100, more preferably 7- 50. Alkenylene refers to a 2-valent aliphatic unsaturated hydrocarbon group with at least one carbon-carbon double bond, and the number of carbon atoms of a straight-chain or branched alkenylene group with a carbon number of 7 or more is, for example, 7 to 200. , preferably 7~100, more preferably 7~50.

Specific examples of the divalent group represented by the formula (b1) include the divalent group represented by the following formula:

[In the formula, * represents a bond site].

A ² each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms (that is, when it has an aliphatic chain, among those aliphatic chains, the number of carbon atoms in the aliphatic chain with the largest number of carbon atoms is 6 or less divalent organic groups). The skeleton atom of the "divalent organic group" represented by A ² is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. The number of skeleton atoms is not particularly limited, for example, it can be 5~3000, 5~1000, 5~ 100, 5~50, etc. A ² may be, for example, a divalent group obtained by removing two amine groups from a diamine compound generally used as a raw material of polyimide without an aliphatic chain having 7 or more carbon atoms, but it is not particularly limited.

A ² is each independently preferably a divalent organic group that does not have an aliphatic chain with 7 or more carbon atoms, and has an aromatic ring and/or a non-aromatic ring (that is, when it has an aliphatic chain, among those aliphatic chains , the number of carbon atoms in the aliphatic chain with the largest number of carbon atoms is 6 or less, and has an aromatic ring and/or a non-aromatic ring divalent organic group), more preferably formula (b2):

[In the formula, Y ²¹ each independently represents a single bond, or -C(R ^x ) ₂ - (preferably -C(R ^x ) ₂ -); Y ²² each independently represents a single bond, -C(R ^y ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO- (preferably -C(R ^y ) ₂ - or -O-); R Each of ^x and R ^y independently represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group (preferably a hydrogen atom); each of the rings Z ^y2 independently represents a group which may have an alkyl group selected from 1 to 6 carbon atoms and a phenyl group The non-aromatic ring of , or an aromatic ring that may have a base selected from an alkyl group with 1 to 6 carbon atoms and a phenyl group, e represents an integer of 0 or more (preferably an integer of 0 or 1 to 5); * Represents a divalent group represented by a bonding site]. In addition, each unit of e-unit may be the same or different.

Specific examples of the divalent group represented by the formula (b2) include the divalent group represented by the following formula:

[In the formula, * represents a bond site].

B ¹ each independently represents a tetravalent organic group having an aromatic ring and/or a non-aromatic ring. ^The skeleton atom of the "tetravalent organic group" represented by B1 is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. ~100, 5~50, etc. For example, B1 can be ^a tetravalent group obtained by removing two acid anhydride groups (-CO-O-CO-) from tetracarboxylic anhydrides having an aromatic ring and/or a non-aromatic ring generally used as a raw material of polyimide , but not particularly limited.

B ¹ are each independently preferably a tetravalent organic group that does not have an aliphatic chain with 7 or more carbon atoms and has an aromatic ring and/or a non-aromatic ring (that is, when it has an aliphatic chain, the The number of carbon atoms in the aliphatic chain with the largest number of carbon atoms is 6 or less, and has an aromatic ring and/or a non-aromatic tetravalent organic group), more preferably the formula (b3):

[In the formula, R ¹ each independently represents an alkyl group or phenyl group with 1 to 6 carbon atoms; X ¹ each independently represents a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S- , -SO-, -SO ₂ -, -CONH-, or -NHCO- (preferably -C(R ^z ) ₂ - or -O-); R ^z each independently represents a hydrogen atom, methyl, ethyl or Phenyl (preferably a hydrogen atom); each of the rings Z ^x1 independently represents a non-aromatic ring that may have a group selected from an alkyl group with 1 to 6 carbon atoms and a phenyl group, or may have a group selected from 1 to 6 carbon atoms The aromatic ring of the alkyl group and the phenyl group; a each independently represents an integer of 0~2 (preferably 0); b represents 0 or 1; c represents an integer of 0 or more (preferably 0 or 1~ Integer of 5); * represents the tetravalent group represented by the bonding site]. In addition, the a unit and the c unit may be the same or different from each other.

Specific examples of the tetravalent group represented by the formula (b3) include the tetravalent group represented by the following formula:

[In the formula, * represents a bond site].

In one embodiment, the maleimide compound of (B) component is more preferably formula (B2):

[In the formula, each symbol system is the same as the formula (B1), (b1), (b2) and (b3)] The compound represented (the bond between the n1 unit and the n2 unit) is more preferably the formula (B3):

[In the formula, each symbol system is the same as the formula (B1), (b2) and (b3)] The compound represented (the bond between the n1 unit and the n2 unit is a bond).

Specific examples of the (B) component include, for example, formulas (B4-1) to (B4-5):

[In the formula, n1' and n2' each independently represent an integer of 1 to 20 (preferably an integer of 1 to 10)] Said maleimide compound. The order and arrangement of the n1' units and the n2' units are arbitrary, and include alternating copolymers, block copolymers, random copolymers, and the like.

The weight average molecular weight (Mw) of the component (B) is not particularly limited, but is preferably 200 to 50,000, more preferably 300 to 40,000, and still more preferably 400 to 20,000. The weight average molecular weight of the component (B) can be measured in terms of polystyrene by a gel permeation chromatography (GPC) method.

(B) As a commercial item of a component, "BMI-689", "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-2500" by Designer molecules, etc. are mentioned, for example.

The content of the (B) component in the resin composition is not particularly limited, but when the non-volatile matter in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably It is 30 mass % or less, More preferably, it is 25 mass % or less, Especially preferably, it is 20 mass % or less. The lower limit of the content of the component (B) in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and More preferably, it is 5 mass % or more, still more preferably 10 mass % or more, and particularly preferably 15 mass % or more.

<(C) Maleimide compound having no aliphatic chain having 7 or more carbon atoms> The resin composition of this invention contains the maleimide compound which does not have an aliphatic chain with 7 or more carbon atoms as components other than (B) (C). That is, when the component (C) has an aliphatic chain, the aliphatic chain having the largest number of carbon atoms among those aliphatic chains has 6 or less carbon atoms. (C) A component may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

In one embodiment, the component (C) preferably has a maleimide group directly bonded to a carbon atom constituting an aromatic ring, and the maleimide group contained in the component (C) is particularly preferably only directly A maleimide group bonded to a carbon atom constituting an aromatic ring.

In one embodiment, the maleimide compound of component (C) preferably contains formula (C1-1) or (C1-2):

[In the formula, B ² each independently represents a tetravalent organic group that does not have an aliphatic chain with 7 or more carbon atoms; n represents an integer of 1 or more (preferably an integer of 1 to 100); A ³ each independently represents no Divalent organic group of aliphatic chain with 7 or more carbon atoms; R ³ each independently represents an alkyl group or phenyl group with 1 to 6 carbon atoms; s represents an integer of 1 or more (preferably 1 or 1 to 100 The integer of t is preferably 1 or an integer of 1-50, and more preferably an integer of 1 or 1-20); t independently represents an integer of 0-2 (preferably 0); other symbols are the same as those of the formula ( B1) is the same as the maleimide compound represented by]. In addition, the units of n, s, and t may be the same or different from each other.

B2 each independently represents a tetravalent organic group that does not have an aliphatic chain with a carbon number of ⁷ or more (that is, when there is an aliphatic chain, the carbon number of the aliphatic chain with the highest carbon number among those aliphatic chains is 6 the following tetravalent organic group). The skeleton atom of the "tetravalent organic group" represented by B ² is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. ~100, 5~50, etc. For example, B2 can be obtained by removing ^two acid anhydride groups (-CO-O-CO-) from tetracarboxylic acid anhydride generally used as a raw material of polyimide without an aliphatic chain with 7 or more carbon atoms A tetravalent base is not particularly limited.

B ² are each independently preferably a tetravalent organic group that does not have an aliphatic chain with 7 or more carbon atoms, and has an aromatic ring and/or a non-aromatic ring (that is, when it has an aliphatic chain, among those aliphatic chains The aliphatic chain having the largest number of carbon atoms has 6 or less carbon atoms and a tetravalent organic group having an aromatic ring and/or a non-aromatic ring), more preferably a tetravalent group represented by the above formula (b3).

A ³ each independently represents a divalent organic group that does not have an aliphatic chain having 7 or more carbon atoms. The skeleton atom of the "divalent organic group" represented by A ³ is, for example, selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. ~100, 1~50, etc.

The maleimide compound represented by the formula (C1-1) is preferably the formula (C2-1):

[In the formula, each symbol system is the same as the formula (C1-1), (b2) and (b3)] The maleimide compound represented by the formula is more preferably the formula (C3-1):

[In the formula, R ² each independently represents an alkyl group or phenyl group with 1 to 6 carbon atoms; f each independently represents an integer of 0 to 2; other symbols are the same as those of formulae (C1-1), (b2) and (b3) )same. ] represents the maleimide compound. In addition, each unit of the f unit system may be the same or different.

The maleimide compound represented by the formula (C1-2) is preferably the formula (C2-2):

[wherein, X ³ each independently represents a single bond, -C(R ^a ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO- R ^a each independently represents a hydrogen atom, a methyl group, an ethyl group or a phenyl group; the ring Z ^x3 represents a non-aromatic ring that may have a base selected from an alkyl group with 1 to 6 carbon atoms and a phenyl group, or may have a group selected from the group consisting of: Aromatic rings of alkyl groups with 1 to 6 carbon atoms and phenyl groups; u each independently represents an integer of 0 or more (preferably an integer of 0 or 1 to 50); other symbols are the same as those of the formula (C1- 2) The maleimide compound represented by the same], more preferably, the formula (C3-2):

[wherein, X ⁴ each independently represents a single bond, -C(R ^b )(R ^c )-, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO-; R ⁴ and R ^b each independently represent a hydrogen atom, a methyl group or a phenyl group; R ⁵ each independently represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms or a phenyl group, and R ^c represents a hydrogen atom, a methyl group Or phenyl, or R ⁵ and R ^c are bonded together to form a ring (for example, an indan ring) that can have a group selected from an alkyl group and an alkenyl group. R ⁶ each independently represents a hydrogen atom, a group of 1 to 6 carbon atoms. An alkyl group or a phenyl group; v represents an integer of 0 or more (preferably an integer of 0 or 1 to 10); other symbols are the same as the maleimide compounds represented by the formula (C1-2). In addition, the u unit and the v unit may be the same or different from each other.

The specific example of (C) component, for example, formula (C4-1)～(C4-4) can be mentioned:

[In the formula, n' and n" each independently represent an integer of 1-20 (preferably an integer of 1-10); s' represents an integer of 1-100 (preferably an integer of 1-50, more preferably 1 ~20 integer); v' each independently represents an integer from 1 to 10 (preferably an integer from 1 to 5)] Said maleimide compound. The order and arrangement of the n' units and n" units are arbitrary, and include alternating copolymers, block copolymers, random copolymers, and the like.

The weight average molecular weight (Mw) of the component (C) is not particularly limited, but is preferably 200 to 50,000, more preferably 300 to 40,000, and even more preferably 400 to 20,000. The weight average molecular weight of the component (C) can be measured in terms of polystyrene by a gel permeation chromatography (GPC) method.

As a commercial item of (C) component, "BMI-6100" by Designer Molecules Co., Ltd., "MIR-3000-70MT" by Nippon Kayaku Co., Ltd., etc. are mentioned, for example.

The content of the component (C) in the resin composition is not particularly limited, but when the non-volatile matter in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably It is 30 mass % or less, More preferably, it is 25 mass % or less, Especially preferably, it is 20 mass % or less. The lower limit of the content of the component (C) in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and More preferably, it is 5 mass % or more, still more preferably 10 mass % or more, and particularly preferably 15 mass % or more.

In the resin composition, the mass ratio of (C) component to (B) component ((C) component/(B) component) is not particularly limited, but is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably 0.5 or more, particularly preferably 0.8 or more. The upper limit of the mass ratio ((C)component/(B)component) of the component (C) to the component (B) is not particularly limited, but is preferably 50 or less, more preferably 40 or less, and still more preferably 20 Hereinafter, 5 or less is particularly preferred.

In the resin composition, the mass ratio of (A) component to the total of (B) component and (C) component ((A) component/(B) component and (C) component total) is not particularly limited, but is preferably It is 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and particularly preferably 0.2 or more. The upper limit of the mass ratio of (A) component to the total of (B) component and (C) component ((A) component/(B) component and (C) component total) is not particularly limited, but preferably 5 or less , more preferably 1 or less, still more preferably 0.5 or less, particularly preferably 0.3 or less.

<(D) Arbitrary radical polymerizable compound> The resin composition of the present invention may contain (D) radically polymerizable compounds other than (B) component and (C) component as optional components. (D) A component may be used individually by 1 type, and may be used in arbitrary combination of 2 or more types.

(D)component may be a compound which has a radically polymerizable unsaturated group, for example. The radically polymerizable unsaturated group is not particularly limited when it can be radically polymerized, and is preferably an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or inside, and specifically, allyl, 3- Unsaturated aliphatic groups such as cyclohexenyl; aromatic groups containing unsaturated aliphatic groups such as p-vinylphenyl, m-vinylphenyl, styryl, etc.; acrylyl, methacryloyl α, β-unsaturated carbonyl groups such as base, maleic acid group, fumaric acid group, etc. The component (D) preferably has one or more radically polymerizable unsaturated groups, more preferably two or more.

As the component (D), known radically polymerizable compounds can be widely used without particular limitation, and examples thereof include (D-1) vinylphenyl-based radically polymerizable compounds and (D-2) (meth)acrylic acid. Radical polymerizable compounds, etc.

<(D-1) Vinylphenyl-based radically polymerizable compound> (D-1) The vinylphenyl-based radically polymerizable compound is a radically polymerizable compound having a vinylphenyl group. The vinylphenyl-based radically polymerizable compound preferably has two or more vinylphenyl groups in one molecule.

In one embodiment, the (D-1) vinylphenyl-based radically polymerizable compound is preferably a vinylbenzyl-modified polyphenylene ether having a vinylbenzyl group and a polyphenylene ether skeleton, and particularly preferably has the formula (D1):

[wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group)] Repetitive unit represented by (repetitive unit number, preferably 2~300, more preferably 2~100) and vinylbenzyl modified polyphenylene ether with vinylbenzyl group (especially the hydrogen atoms of the hydroxyl groups at both ends of the polyphenylene ether are replaced with vinyl groups Both ends of the benzyl group are vinylbenzyl modified polyphenylene ether).

In other embodiments, the (D-1) vinylphenyl-based radically polymerizable compound preferably has the formula (D2):

[In the formula, R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom)] Divinylbenzene polymerization of repeating units (the number of repeating units, preferably 2 to 200) thing. The divinylbenzene polymer may be a copolymer having other styrene skeleton units such as a styrene unit, an ethylstyrene unit, or the like. When it has other styrene skeleton unit, it is preferable that the ratio of the repeating unit of formula (D2) is 5-70 mol% with respect to all styrene skeleton units.

(D-1) The number-average molecular weight of the vinylphenyl-based radically polymerizable compound is not particularly limited, but is preferably 500 to 100,000, more preferably 700 to 80,000. The number-average molecular weight of the component (D) can be measured in terms of polystyrene by a gel permeation chromatography (GPC) method. (D-1) The functional group equivalent of the vinyl group of the vinylphenyl-based radically polymerizable compound is not particularly limited, but is preferably 200 g/eq. to 3000 g/eq., more preferably 200 g/eq. to 2000 g /eq..

(D-1) Commercial products of vinylphenyl-based radically polymerizable compounds include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified poly Phenyl ether); "ODV-XET-X03", "ODV-XET-X04", "ODV-XET-X05" (divinylbenzene polymer) manufactured by NIPPON STEEL Chemical & Material Co., Ltd.

<(D-2) (Meth)acrylic radical polymerizable compound> (D-2) The (meth)acrylic radical polymerizable compound is a radical polymerizable compound having an acryl group and/or a methacryl group. (D-2) The (meth)acrylic radical polymerizable compound preferably has two or more acryl group and/or methacryl group in one molecule. (D-2) A (meth)acrylic radical polymerizable compound, preferably a (meth)acrylic modified polyphenylene ether having an acryl group and/or a methacryloyl group and a polyphenylene ether skeleton, especially It is better to have the formula (D3):

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or a substituent (preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a methyl group)] Repetitive unit represented by (repetitive unit number, preferably 2 to 300, more preferably 2 to 100) and acrylyl and/or methacryloyl (meth)acrylic modified polyphenylene ether (especially the hydroxyl groups at both ends of the polyphenylene ether) The hydrogen atoms of , are substituted with acrylyl and/or methacrylyl groups at both ends (meth)acrylic acid-modified polyphenylene ether).

(D-2) The number average molecular weight of the (meth)acrylic radical polymerizable compound is not particularly limited, but is preferably 500 to 10,000, more preferably 700 to 5,000. (D-2) The functional group equivalents of the acryl group and the methacryl group of the (meth)acrylic radically polymerizable compound are not particularly limited, but are preferably 200 g/eq. to 3000 g/eq., more preferably It is 300g/eq.~2000g/eq..

(D-2) Commercial products of the (meth)acrylic radical polymerizable compound include, for example, "SA9000" and "SA9000-111" (methacrylic acid-modified polyphenylene ether) manufactured by SABIC Innovative Plastics. .

The content of the component (D) in the resin composition is not particularly limited, but when the non-volatile matter in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably It is 40 mass % or less, More preferably, it is 30 mass % or less, Especially preferably, it is 20 mass % or less. The lower limit of the content of component (D) in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, for example, it can be 0% by mass, 0.1% by mass or more, 1% by mass or more, 3% by mass or more. mass % or more, 5 mass % or more, 7 mass % or more, etc.

<(E) Inorganic fillers> The resin composition of the present invention contains (E) an inorganic filler as an optional component. (E) The inorganic filler is contained in the resin composition in a particle state.

(E) As the material of the inorganic filler, an inorganic compound is used. (E) Materials for the inorganic filler include, for example, silica, alumina, glass, lapis lazuli, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, hydrated aluminum Stone, 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, titanium Bismuth acid, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstate, ferric iron, iron alloys, etc. Of these, particularly preferred is silicon dioxide. Silica includes, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Also, the silica is preferably spherical silica. (E) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

(E) Commercial products of inorganic fillers include, for example, "UFP-30" manufactured by Denka Chemical Industries, Ltd.; "SP60-05" and "SP507-05" manufactured by NIPPON STEEL & SUMIKIN MATERIALS; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka Corporation; "SilFileNSS-3N", "SilFileNSS-4N", "SilFileNSS-5N" manufactured by Tokuyama Corporation ; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" made by admatechs company; "DAW-03", "FB-105FD" made by Denka company, etc.

(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 2 μm or less, still more preferably 1 μm or less, and particularly preferably 0.7 μm or less. (E) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (E) The average particle size of the inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size can be measured as an average particle size. As the measurement sample, one that weighs 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a small glass bottle and disperses it with ultrasonic waves for 10 minutes can be used. Using a laser diffraction particle size distribution measuring device, and using the light source wavelengths as blue and red, the measurement sample is measured by a flow battery method to measure the volume-based particle size distribution of the inorganic filler, and from the obtained particle size distribution, as The median particle diameter was used to calculate the average particle diameter. As a laser diffraction particle size distribution measuring apparatus, "LA-960" manufactured by Horiba, Ltd., etc. is mentioned, for example.

(E) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, still more preferably 1 m ² /g or more, and particularly preferably 3 m ² /g or more g or more. (E) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, still more preferably 50 m ² /g or less, particularly preferably 40 m ² /g g or less. The specific surface area of the inorganic filler was obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH Co., Ltd.) according to the BET method, adsorbing nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

(E) The inorganic filler is preferably surface-treated with an appropriate surface-treating agent. The moisture resistance and dispersibility of the (E) inorganic filler can be improved by surface treatment. Examples of surface treatment agents include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Epoxy silane coupling agents such as glycidoxypropyltriethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; 3-methacryloyloxypropyl Methyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyl Methacryloyl-based silane coupling agents such as triethoxysilane; acrylic silane coupling agents such as 3-acryloyloxypropyltrimethoxysilane; N-2-(aminoethyl)-3 -aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Propyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane , N-phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc. Mixtures; isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane, etc. Mixtures; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.; isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane; Anhydride-based silane coupling agents such as 3-trimethoxysilylpropyl succinic anhydride; etc. silane coupling agents; methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyl Triethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane Non-silane-coupled-alkanes of ethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc. Oxysilane compounds, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

Commercially available surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", " "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styryl silane coupling agent); "KBM-502", "KBM-503" ", "KBE-502", "KBE-503" (methacryloyl silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amine-based silane coupling agent); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (urea-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent) ; "X-12-967C" (acid anhydride silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103" ", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" ( non-silane coupling-alkoxysilane compounds), etc.

The degree of surface treatment by the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, the inorganic filler is 100% by mass, preferably 0.2% by mass to 5% by mass of the surface treatment agent, more preferably 0.2% by mass to 3% by mass, and more preferably 0.2% by mass to 3% by mass. 0.3 mass % to 2 mass % are surface-treated.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content 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 still more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. ² or more. In addition, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity of the sheet form, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg/m ² or less. .

The surface-treated inorganic filler can be washed with a solvent (eg, methyl ethyl ketone (MEK)), and then (E) the amount of carbon per unit surface area of the inorganic filler can be measured. Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface-treating agent, followed by ultrasonic cleaning 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 a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

The content of the (E) inorganic filler in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 90% by mass or less, more preferably 80% by mass or less , more preferably 75 mass % or less, and particularly preferably 70 mass % or less. The lower limit of the content of the (E) inorganic filler in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, for example, it may be 0% by mass or more, 1% by mass or more, and 5% by mass or more. % or more, 10 mass % or more, etc., preferably 20 mass % or more, more preferably 25 mass % or more, still more preferably 35 mass % or more, particularly preferably 40 mass % or more.

<(F) Hardening accelerator> The resin composition of the present invention may contain (F) a curing accelerator as an optional component. In one embodiment, the hardening accelerator (F) may have a catalyst that promotes the addition reaction of the component (A), the component (B), the component (C) (and the component (D) when the component (D) is included), etc. function.

(F) Curing accelerators, for example, (F-1) imidazole-based curing accelerators, (F-2) phosphorus-based curing accelerators, (F-3) urea-based curing accelerators, (F-4) guanidine-based curing accelerators Hardening accelerators, (F-5) metal-based hardening accelerators, (F-6) amine-based hardening accelerators, and the like. In one embodiment, the (F) curing accelerator preferably contains (F-1) an imidazole-based curing accelerator. (F) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

(F-1) Imidazole-based hardening accelerators, for example, 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 yl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4 -Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4 '-Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s -Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl -5-Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride , 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resins.

(F-1) Imidazole-based hardening accelerator, commercially available products can be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemical Co., Ltd., "P200" manufactured by Mitsubishi Chemical Co., Ltd. -H50" etc.

(F-2) Phosphorus-based curing accelerator, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium lauric acid Esters, bis(tetrabutylphosphonium) pyromellitic acid ester, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl) Aliphatic phosphonium salts such as methyl]-4-methylphenolate (Phenolate), di-tert-butylmethylphosphonium tetraphenylborate, etc.; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide , propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylboronic acid salt, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenyl borate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate , Aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine-borane complexes such as triphenylphosphine, triphenylborane, etc.; triphenylphosphine, p-benzoquinone, etc. Aromatic phosphine and quinone addition reactants such as reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di- Aliphatic phosphines such as tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, etc.; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine Phosphine, Ethyldiphenylphosphine, Butyldiphenylphosphine, Diphenylcyclohexylphosphine, Triphenylphosphine, Tris-o-Tolylphosphine, Tris-m-Tolylphosphine, Tris-p-Tolylphosphine phosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-isopropylphenyl)phosphine -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(diphenyl) Aromatic phosphines such as phosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, and the like.

(F-3) Urea-based hardening accelerators, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3- Aliphatic dimethyl urea such as cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3 -(4-Chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylurea phenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-di Methyl urea, 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-methoxy Phenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trimethylurea Fluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4 Aromatic dimethylurea such as -methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc.

(F-4) A guanidine-based curing accelerator, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, and 1-(o-tolyl) Guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methylguanidine yl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl Biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide and the like.

(F-5) Metal-based hardening accelerators include, for example, 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 acetylacetonate (II), cobalt acetylacetonate (III), etc., organocopper complexes such as copper acetylacetonate (II), etc. Organozinc complexes such as zinc (II) acetylacetonate, organoiron complexes such as iron (III) acetylacetonate, organonickel complexes such as nickel (II) acetylacetonate, manganese (II) acetylacetonate ) and other organic manganese complexes, etc. The organic metal salts include, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

(F-6) Amine-based hardening accelerators, such as triethylamine, tributylamine and other trialkylamines, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6,-Tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

(F-6) As an amine-based hardening accelerator, a commercial item can be used, for example, "MY-25" manufactured by ajinomoto-fine-techno company, etc. are mentioned.

The content of the (F) hardening accelerator in the resin composition is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, and More preferably, it is 3 mass % or less, and particularly preferably 1 mass % or less. The lower limit of the content of the (F) hardening accelerator in the resin composition is not particularly limited, and when the nonvolatile content in the resin composition is 100% by mass, for example, it may be 0% by mass or more, 0.001% by mass or more, and 0.01% by mass. % or more, 0.1 mass % or more, 0.5 mass % or more, etc.

<(G) Other additives> The resin composition of the present invention may contain optional additives as nonvolatile components. Examples of such additives include curing agents other than the component (A) such as phenol-based curing agents and thiol-based curing agents; epoxy resins, epoxy acrylate resins, urethane acrylate resins, and urethane resins. Thermosetting resins such as ester resins, cyanate ester resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, polysiloxane resins, phenoxy resins, etc.; peroxide-based radical polymerization Radical polymerization initiators such as initiators, azo radical polymerization initiators, etc.; Thermoplastic resins such as ester resins, polyetheretherketone resins, polyester resins, etc.; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, organic cobalt compounds; phthalocyanine blue, phthalocyanine green, Coloring agents for iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc.; polymerization inhibitors for hydroquinone, catechol, pyrogallol, phenothiazine, etc.; polysiloxane-based leveling agent, Acrylic polymer-based leveling agent and other flattening agents; Benton, microcrystalline kaolinite and other tackifiers; polysiloxane-based defoamer, acrylic-based defoamer, fluorine-based defoamer, vinyl resin-based defoamer Defoamers such as benzotriazole-based UV absorbers; UV absorbers such as benzotriazole-based UV absorbers; adhesion promoters such as urea silanes; Adhesion-imparting agents such as adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants, hindered amine-based antioxidants, etc.; optical brighteners such as stilbene derivatives; fluorine-based surfactants, polysiloxane-based Surfactants such as surfactants; phosphorus-based flame retardants (such as phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic flame retardants Flame retardants such as flame retardants (such as antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, polysiloxane dispersants, anionic dispersants, cationic dispersants Dispersants such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic acid anhydride stabilizers, etc. Stabilizers, etc. (G) Other additives may be used alone or in combination of two or more in any ratio. (G) The content of other additives can be appropriately set as long as those skilled in the art are skilled in the art.

<(H) Organic solvent> The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the above-mentioned nonvolatile components. (H) As an organic solvent, a well-known thing can be used suitably, and the kind is not specifically limited. (H) Organic solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, acetic acid Ester solvents such as isopentyl, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl Ether, diphenyl ether and other ether solvents; methanol, ethanol, propanol, butanol, ethylene glycol and other alcohol solvents; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, ethyl diethylene glycol acetate, γ-butyrolactone, methyl methoxypropionate and other ether ester solvents; methyl lactate, ethyl lactate, 2-hydroxyisobutyl Ester alcohol solvents such as methyl acid; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) ) and other ether alcohol-based solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide-based solvents; dimethylsulfoxide Nitrile-based solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, methylcyclohexane, etc.; benzene, toluene, xylene, ethyl Aromatic hydrocarbon solvents such as benzene, trimethylbenzene, etc. (H) An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

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

<Manufacturing method of resin composition> In the resin composition of the present invention, for example, in an arbitrary preparation container, (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, (C) Maleimide compound not having an aliphatic chain having 7 or more carbon atoms, (D) optional radical polymerizable compound if necessary, (E) inorganic filler if necessary, (F) hardening if necessary Accelerator, (G) other additives if necessary, and (H) organic solvent if necessary, are added and mixed in any order, and/or a part or all of them are simultaneously added and mixed to manufacture. In addition, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and/or cooling can be performed temporarily or throughout. In addition, in the process of adding and mixing, or after that, the resin composition can be uniformly dispersed by stirring or shaking the resin composition using, for example, a stirring device such as a mixer or a shaking device. In addition, the defoaming may be performed under low pressure conditions such as under vacuum while stirring or shaking.

<Characteristics of resin composition> The resin composition of the present invention comprises (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) a Maleimide compounds with aliphatic chains above 7. By using such a resin composition, a cured product having low specific capacitance (Dk) and dielectric tangent (Df) and excellent peel strength of the plated conductor layer can be obtained.

The cured product of the resin composition of the present invention can have a low dielectric tangent (Df). Therefore, in one embodiment, as in Test Example 1 below, the dielectric tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 0.020 or less, 0.010 or less, more preferably 0.020 or less. It is 0.008 or less, 0.007 or less, more preferably 0.006 or less, 0.005 or less, particularly preferably 0.004 or less, 0.003 or less.

The cured product of the resin composition of the present invention may have a low specific capacitance (Dk). Therefore, in one embodiment, as in Test Example 1 below, the specific capacitance (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 5.0 or less, more preferably 4.0 or less, Still more preferably, it is 3.5 or less, still more preferably 3.0 or less, and particularly preferably 2.9 or less.

The cured product of the resin composition of the present invention can have excellent peel strength of the electroplated conductor layer. Therefore, in one embodiment, as in Test Example 2 below, the cured product forms a copper-plated conductor layer, and the copper-plated peel strength calculated from the load when the copper-plated conductor layer is peeled off in the vertical direction is preferably 0.2 kgf/cm or more. , more preferably 0.3kgf/cm or more, still more preferably 0.35kgf/cm or more, and particularly preferably 0.4kgf/cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf/cm or less.

In one embodiment, the cured product of the resin composition of the present invention may have a feature of low arithmetic mean roughness (Ra) of the surface after roughening treatment. Therefore, in one embodiment, as in the following Test Example 2, the arithmetic mean roughness (Ra) of the surface of the cured product after the roughening treatment measured is preferably 300 nm or less, more preferably 200 nm or less, and more preferably 200 nm or less. It is 150 nm or less, more preferably 120 nm or less, and particularly preferably 100 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more, or the like.

<Application of resin composition> The resin composition of the present invention is suitable for use as a resin composition for insulating purposes, especially a resin composition for forming an insulating layer. Specifically, it can be suitably used as the resin composition for forming the insulating layer (the resin composition for forming the insulating layer for forming the conductor layer) for forming the conductor layer (including the rewiring layer) formed on the insulating layer. Moreover, in the printed wiring board mentioned later, it can be used suitably as the resin composition for insulating layer formation of a printed wiring board (the resin composition for insulating layer formation of a printed wiring board). The resin composition of the present invention can be widely used in sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die-bonding materials, semiconductor packaging materials, buried-hole resins, and parts-embedded resins. Use of resin compositions.

Further, for example, when a semiconductor chip package is produced through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring forming layer for forming an insulating layer for a rewiring layer (resin composition for rewiring formation layer formation), and resin composition for semiconductor wafer encapsulation (resin composition for semiconductor wafer encapsulation) are used. When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) the step of laminating the temporary fixing film on the base material, (2) the step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) the step of forming the sealing layer on the semiconductor wafer, (4) the step of peeling off the base material and the temporary fixing film from the semiconductor wafer, (5) a step of forming a rewiring formation layer as an insulating layer on the surface of the peeled-off base material of the semiconductor wafer and the temporarily fixed thin film, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

In addition, the resin composition of the present invention provides an insulating layer with good component embeddability, so it is suitable for use in a case where the printed wiring board is a component embeddable circuit board.

<Laminated sheet material> The resin composition of the present invention can also be used by coating in a varnish state, and industrially, it is generally suitable for use in the form of a sheet-like laminate containing the resin composition.

The sheet-like laminate material is preferably a resin sheet or a prepreg shown below.

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

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm from the viewpoint of providing a cured product excellent in insulating properties even when the printed wiring board is thinned and the cured product of the resin composition is a thin film the following. The lower limit of the thickness of the resin composition layer is not particularly limited, but it is usually 5 μm or more, 10 μm or more, or the like.

Examples of the support include films, metal foils, and release papers made of plastic materials, and preferably films and metal foils made of plastic materials.

When a film made of a plastic material is used as the support, the plastic material includes, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PET"). Polyester such as "PEN"), polycarbonate (sometimes referred to as "PC" hereinafter), acrylic acid such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC) , polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using a metal foil as a support body, a copper foil, an aluminum foil, etc. are mentioned, for example, a copper foil is preferable. As the copper foil, a foil composed of a single metal of copper, or a foil composed of an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

The surface where the support and the resin composition layer are bonded may be subjected to matting treatment or corona treatment.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined to the resin composition layer can also be used. The mold release agent used for the mold release layer of the mold release layer-attached support includes, for example, one or more selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. release agent. As the support with a release layer, a commercially available product can be used, for example, a PET film having a release layer containing an alkyd resin-based release agent as a main component, "SK-1" and "AL-5" manufactured by Lintec Co., Ltd. ", "AL-7"; "lumirror T60" made by Toray; "Purex" made by Teijin; "unipeel" made by unitika, etc.

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

In one embodiment, the resin sheet may further contain an arbitrary layer if necessary. The optional layer includes, for example, a protective film provided on the surface of the resin composition layer not joined to the support (that is, the surface opposite to the support), depending on the support. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dirt or the like to the surface of the resin composition layer or scratches.

The resin sheet, such as a liquid resin composition, can be used as it is, or a resin varnish prepared by dissolving the resin composition in an organic solvent can be applied to a support using a die coater, etc., and dried to form a resin composition layer. to manufacture.

As the organic solvent, the same ones as those described as components of the resin composition can be exemplified. The organic solvent may be used alone or in combination of two or more.

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

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, the protective film can be peeled off and used later.

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

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

The prepreg can be produced by a conventional method such as a hot melt method and a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned resin sheet.

The sheet-like laminate material of the present invention is suitable for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and is suitable for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

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

The printed wiring board can be manufactured by a method including the steps of the following (I) and (II) using, for example, the above-mentioned resin sheet. (1) The method of bonding the resin composition layer of the resin sheet to the inner-layer substrate on the inner-layer substrate, and the step of laminating the resin sheet (II) Step of curing the resin composition layer (eg, thermosetting) to form an insulating layer

The "inner layer substrate" used in step (I) refers to a member that becomes a substrate of a printed wiring board, such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting type Polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one side or both sides, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, when manufacturing a printed wiring board, further, an intermediate product having an insulating layer and/or a conductor layer formed thereon is also included in the so-called "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner-layer substrate with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding of the resin sheet to the inner layer substrate from the support side. The member for thermocompression bonding of the resin sheet to the inner layer substrate (hereinafter referred to as "thermocompression bonding member") includes, for example, a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), and the like. In addition, instead of pressing the thermocompression-bonding member directly on the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate.

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

Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressurization type|mold laminator by Meiki Seisakusho Co., Ltd., the vacuum coater by Nikko-Materials Co., Ltd., the batch type vacuum pressurization lamination machine, etc. are mentioned, for example.

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

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

In step (II), the resin composition layer is cured (eg, thermally cured) to form an insulating layer composed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and generally used conditions can be used when forming the insulating layer of the printed wiring board.

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

Before thermally curing the resin composition layer, the resin composition layer may be pre-heated at a temperature lower than the curing temperature. For example, before thermosetting the resin composition layer, the resin composition layer may be preliminarily heated for 5 minutes or more at a temperature of 50°C to 120°C, preferably 60°C to 115°C, and more preferably 70°C to 110°C. It is preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer can be further carried out. These steps (III) to (V), for those skilled in the art for the manufacture of printed wiring boards, can be implemented according to various known methods. In addition, when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) between step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeated to form a multilayer wiring board.

In other embodiment, the printed wiring board of this invention can be manufactured using the said prepreg. The manufacturing method is basically the same as the case of using the resin sheet.

Step (III) is a step of opening holes in the insulating layer, whereby holes such as via holes, through holes, etc. can be formed in the insulating layer. The step (III) can be implemented by using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used for forming the insulating layer. The size or shape of the holes can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Typically, in this step (IV), the smear is removed. The order and conditions of the roughening treatment are not particularly limited, and when the insulating layer of the printed wiring board is formed, well-known procedures and conditions generally used can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

The swelling liquid that can be used in the roughening step is not particularly limited, and examples thereof include alkali solutions, surfactant solutions, etc., preferably alkali solutions, and more preferably sodium hydroxide solutions and potassium hydroxide solutions. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment by the swelling liquid is not particularly limited, but for example, the insulating layer is immersed 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 a swelling liquid of 40° C. to 80° C. for 5 minutes to 15 minutes.

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

In addition, the neutralizing liquid used for the roughening treatment is preferably an acidic aqueous solution, and as a commercial product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan can be mentioned.

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

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

The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, formed of two or more metal alloys (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) selected from the above-mentioned group. formed layer. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a single metal layer of nickel, from the viewpoints of versatility, cost, easiness of patterning, etc., for forming the conductor layer is preferred. •Alloy layer of chromium alloy, copper•nickel alloy, copper•titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel•chromium alloy , and more preferably a single metal layer of copper.

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

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

In one embodiment, the conductor layer can be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, which is preferable from the viewpoint of easiness of manufacture. to be formed by the semi-additive method. Hereinafter, an example in which the conductor layer is formed by the semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed. On the exposed electroplating seed layer, after forming a metal layer by electroplating, the mask pattern is removed. Then, by removing the unnecessary plating seed layer by etching or the like, a conductor layer having a desired wiring pattern can be formed.

In other embodiments, the conductor layer may be formed using metal foil. When the conductor layer is formed using metal foil, the step (V) is preferably performed between the step (I) and the step (II). For example, after the 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 can be carried out by a vacuum lamination method. The conditions for lamination may be the same as those described in step (I). Next, step (II) is carried out to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as a subtractive process and an analog semi-additive method.

The metal foil can be produced by a conventional method such as an electrolytic method and a rolling method, for example. As a commercial item of metal foil, HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil by Mitsui Metal Mining Co., Ltd. made by JX Nippon Mining Co., Ltd., etc. are mentioned, for example.

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

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

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited by these embodiments. In addition, in the following, "part" and "%" indicating the amount, unless otherwise specified, indicate "part by mass" and "% by mass", respectively. In particular, the temperature condition when there is no specified temperature is room temperature (25°C).

<Example 1> 10 parts of an amine compound containing a biphenyl skeleton (“BAN” manufactured by Nippon Kayaku Co., Ltd.), 20 parts of an aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules Co., Ltd.), and an aromatic Maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with a solid content of 70%) 28.6 parts, imidazole-based hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd., 1 part of 1-benzyl-2-phenylimidazole), surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) 60 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.8 m ² /g) were mixed and uniformly dispersed using a high-speed rotary mixer to prepare a resin composition.

<Example 2> Except using 20 parts of aliphatic maleimide compound (“BMI-1500” manufactured by Designer molecules) in place of 20 parts of aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules), the same Example 1 The resin composition was prepared in the same manner.

<Example 3> Except using 20 parts of aliphatic maleimide compound (“BMI-2500” manufactured by Designer Molecules Co., Ltd.) instead of 20 parts of aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules Co., Ltd.) Example 1 The resin composition was prepared in the same manner.

<Example 4> Except using 20 parts of aliphatic maleimide compound (“BMI-3000J” manufactured by Designer Molecules Co., Ltd.) instead of 20 parts of aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules Co., Ltd.) Example 1 The resin composition was prepared in the same manner.

<Example 5> In addition to using 20 parts of an aromatic maleimide compound (“BMI-6100” manufactured by Designer Molecules), instead of an aromatic maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.), 70 parts of solid content % MEK/toluene mixed solution) 28.6 parts, the resin composition was prepared in the same manner as in Example 2.

<Example 6> In addition to using 20 parts of an aromatic maleimide compound (“BMI-6100” manufactured by Designer Molecules), instead of an aromatic maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.), 70 parts of solid content % MEK/toluene mixed solution) 28.6 parts, the resin composition was prepared similarly in Example 3.

<Example 7> In addition to changing the usage amount of the aromatic maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., a MEK/toluene mixed solution with a solid content of 70%) from 28.6 parts to 14.3 parts, an aromatic A resin composition was prepared in the same manner as in Example 2 except for 10 parts of a maleimide compound (“BMI-6100” manufactured by Designer Molecules).

<Example 8> A maleimide compound A represented by the following formula (X) (Mw/Mn=1.81, v”=1.47 was prepared by the method described in Synthesis Example 1 of the Invention Association Publication No. 2020-500211 (mainly 1, 2 or 3)) of MEK solution (non-volatile content 70 mass %).

In addition to using 28.6 parts of an aromatic maleimide compound (maleimide compound A represented by the formula (X), a MEK solution with a solid content of 70% by mass), instead of an aromatic maleimide compound (Nihon Kayaku) A resin composition was prepared in the same manner as in Example 2, except that the company's "MIR-3000-70MT", a MEK/toluene mixed solution with a solid content of 70%) was 28.6 parts.

<Example 9> Except for spherical silica ("SO-C2" manufactured by admatechs, Inc. ”) was changed from 60 parts to 70 parts, and 15.4 parts of vinylbenzyl-modified polyphenylene ether (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a solid content of 65%) was used in addition to 15.4 parts. In Example 2, a resin composition was prepared in the same manner.

<Example 10> Except for spherical silica (“SO-C2” manufactured by Admatechs, Inc.) treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) ”) was changed from 60 parts to 70 parts, and 20 parts of methacrylic acid-modified polyphenylene ether (“SA9000-111” manufactured by SABIC Innovative Plastics Co., Ltd. was used as a toluene solution with a solid content of 50%) was used. A resin composition was prepared in the same manner as in Example 2.

<Example 11> Except for spherical silica (“SO-C2” manufactured by Admatechs, Inc.) treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) ”) was changed from 60 parts to 70 parts, and a divinylbenzene/styrene copolymer (“ODV-XET-X04” manufactured by NIPPON STEEL Chemical & Material Co., Ltd., a toluene solution with a solid content of 65%) was used for 15.4 A resin composition was prepared in the same manner as in Example 2 except for the parts.

<Comparative Example 1> In addition to not using 20 parts of an aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules), an aromatic maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd.), solid A resin composition was prepared in the same manner as in Example 1, except that the usage amount of MEK/toluene mixed solution with a composition of 70%) was changed from 28.6 parts to 57.1 parts.

<Comparative Example 2> In addition to changing the amount of the aliphatic maleimide compound (“BMI-689” manufactured by Designer molecules) from 20 parts to 10 parts, an amine compound without a biphenyl skeleton (“A-A” manufactured by Nippon Kayaku Co., Ltd.) was used. ”) 10 parts, except that 10 parts of the amine compound (“BAN” manufactured by Nippon Kayaku Co., Ltd.) containing a biphenyl skeleton was replaced, a resin composition was prepared in the same manner as in Example 1.

<Test example 1: Measurement of specific capacitance (Dk) and dielectric tangent (Df)> A polyethylene terephthalate film (“AL5” manufactured by Lintec Co., Ltd., thickness 38 μm) provided with a mold release layer was prepared as a support. On the mold release layer of this support, the resin compositions obtained in Examples and Comparative Examples were uniformly coated so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

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

Regarding the cured product B for evaluation, the value of the dielectric constant was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by using “HP8362B” manufactured by Agilent Technologies, Inc. by the Cavity Perturbation Method. (Dk value) and the value of dielectric tangent (Df value). The measurement was performed on two test pieces, and the average was calculated.

<Test example 2: Measurement of peel strength and arithmetic mean roughness (Ra)> (1) Preparation of inner layer substrate On both sides of the epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.4mm, "R1515A" manufactured by Panasonic Corporation) with inner layer circuit support glass cloth base material ”) to etch 1 μm to roughen the copper surface.

(2) Lamination of resin sheet A Using a batch-type vacuum pressure laminator (manufactured by Nikko-Materials, Inc., 2-stage build-up laminator "CVP700"), the resin composition layer was brought into contact with the inner layer substrate, and the resin sheet A obtained in Test Example 1 was laminated on Both sides of the inner substrate. The lamination system was decompressed for 30 seconds, and the air pressure was adjusted to 13 hPa or less, followed by pressure bonding at 120° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Thermosetting of the resin composition layer Then, the inner layer substrate on which the resin sheet A was laminated was put into an oven at 130°C and heated for 30 minutes, then moved into an oven at 190°C and heated for 30 minutes to thermally harden the resin composition layer to form an insulating layer. Then, the support body was peeled off, and the cured board|substrate A which has an insulating layer, an inner-layer board|substrate, and an insulating layer in this order was obtained.

(4) Coarsening treatment The hardened substrate A is subjected to desmear treatment for roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

(Wet degreaser treatment) The cured substrate A was immersed in a swelling solution (“Swelling Dip Securiganth P” manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, followed by an oxidizing agent solution (manufactured by Atotech Japan). "Concentrate Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%), immersed at 80°C for 20 minutes. Next, after immersion for 5 minutes in a neutralizing solution (“Reduction solution Securiganth P” manufactured by Atotech Japan, an aqueous sulfuric acid solution) at 40° C., it was dried at 80° C. for 15 minutes.

(5) Determination of the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment Using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bruker), the surface of the insulating layer of the hardened substrate A after the roughening treatment was obtained from the values obtained by using a VSI mode, a 50x lens, and a measurement range of 121 μm × 92 μm. The arithmetic mean roughness (Ra). The average value of each 10 points was calculated.

(6) Formation of Conductor Layer The conductor layer was formed on the roughened surface of the insulating layer of the hardened substrate A according to the semi-additive method. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Next, after heating at 150° C. for 30 minutes and performing annealing treatment, an etching resist was formed, and a pattern was formed by etching. Then, copper sulfate electroplating was performed to form a conductor layer with a thickness of 25 μm, and annealing treatment was performed at 190° C. for 60 minutes. The obtained board|substrate is called "evaluation board|substrate B".

(7) Determination of peel strength of electroplated conductor layer The peel strength of the insulating layer and the conductor layer was measured according to Japanese Industrial Standards (JIS C6481). Specifically, the conductor layer of the evaluation substrate B was cut at a width of 10 mm and a length of 100 mm, the end was peeled off, and grasped with a gripper. At room temperature, at a speed of 50 mm/min, the vertical direction was measured. The load (kgf/cm) when pulling and peeling 35 mm was used to obtain the peeling strength. The measurement system used a tensile tester ("AC-50C-SL" manufactured by TSE).

The usage-amount of the non-volatile matter of the resin compositions of Examples and Comparative Examples and the measurement results of the test examples are shown in Table 1 below.

In the above, by using (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) no compound having 7 or more carbon atoms The resin composition of the maleimide compound in the aliphatic chain can obtain a cured product with low specific capacitance (Dk) and dielectric tangent (Df) and excellent peel strength of the electroplated conductor layer.

Claims (21)

A resin composition comprising (A) an amine compound having a biphenyl skeleton, (B) a maleimide compound having an aliphatic chain having 7 or more carbon atoms, and (C) A maleimide compound which does not have an aliphatic chain having 7 or more carbon atoms. The resin composition according to claim 1, wherein the component (B) has a maleimide group directly bonded to a carbon atom not constituting an aromatic ring. The resin composition according to claim 1, wherein the component (C) has a maleimide group directly bonded to a carbon atom constituting an aromatic ring. The resin composition according to claim 1, wherein the component (A) has a primary amine group. The resin composition according to claim 1, wherein the component (A) has an amine group directly bonded to a carbon atom constituting an aromatic ring. As the resin composition of claim 1, wherein (A) component comprises formula (A1):

[wherein, V and W each independently represent -C(R') ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO-, R Each independently represents a substituent, R' each independently represents a hydrogen atom or a substituent, and h, i and j each independently represent an integer of 0 to 2] The amine compound represented by the repeating unit. As in the resin composition of claim 1, when the non-volatile matter in the resin composition is set to 100% by mass, the content of component (A) is 3% by mass to 40% by mass. As in the resin composition of claim 1, when the nonvolatile matter in the resin composition is set to 100% by mass, the content of component (B) is 3% by mass to 40% by mass. The resin composition of claim 1, wherein when the non-volatile matter in the resin composition is set to 100% by mass, the content of component (C) is 3% by mass to 40% by mass. The resin composition of claim 1, wherein the mass ratio of (C) component to (B) component ((C) component/(B) component) is 0.5 to 20. The resin composition of claim 1, wherein the mass ratio of component (A) to the total of components (B) and (C) (component (A)/total of components (B) and (C)) is 0.1 ~0.5. The resin composition of Claim 1 which further contains (D) a radical polymerizable compound other than (B) component and (C) component. The resin composition according to claim 1, further comprising (E) an inorganic filler. The resin composition of claim 13, wherein the content of the component (E) is 25 mass % or more when the non-volatile content in the resin composition is 100 mass %. The resin composition of claim 1, wherein the dielectric tangent of the cured product of the resin composition is 0.004 or less when measured at 5.8 GHz and 23°C. The resin composition of claim 1, wherein the specific capacitance of the cured product of the resin composition is 2.9 or less when measured at 5.8 GHz and 23°C. A hardened product, which is the hardened product of the resin composition according to any one of claims 1 to 16. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 16. A resin sheet having a support body and a resin composition layer formed of the resin composition of any one of claims 1 to 16 provided on the support body. A printed wiring board including an insulating layer composed of a cured product of the resin composition of any one of claims 1 to 16. A semiconductor device comprising the printed wiring board of claim 20.