KR20220014836A - Resin composition - Google Patents

Abstract

The present invention provides a resin composition and the like from which a cured product having low dielectric properties, excellent peel strength, and high glass transition temperature even with small surface roughness can be obtained. The resin composition comprises: (A) a polyether ether ketone compound having a maleimide group; (B) an epoxy resin, and (C) an active ester curing agent.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. Moreover, this invention relates to the resin sheet obtained using the said resin composition, a printed wiring board, and a semiconductor device.

As a manufacturing technique of a printed wiring board, the manufacturing method by the buildup method which piles up an insulating layer and a conductor layer alternately is known. In the manufacturing method by a build-up system, generally, an insulating layer hardens a resin composition, and is formed. As such a resin composition, the resin composition disclosed by patent document 1 is known, for example.

[Patent Document 1] Japanese Patent Laid-Open No. 2019-066792

The cured product formed by curing the resin composition can be used as an insulating layer of a printed wiring board of a semiconductor device. Accordingly, it is required to lower the dielectric properties (dielectric constant and dielectric loss tangent) of the cured product. Moreover, even if the roughness of the surface of an insulating layer is small, the insulating layer formed of this hardened|cured material is excellent in the peeling strength between a conductor layer, and also in order to be excellent in heat resistance, it is preferable that a glass transition temperature is high.

This invention was created in view of the said subject, It is a resin composition from which a hardened|cured material with a high glass transition temperature can be obtained which is excellent in peeling strength even if a dielectric property is low and surface roughness is small; a resin sheet comprising a resin composition layer comprising the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board. aims to provide

As a result of the present inventor earnestly examining in order to solve the said subject, this inventor uses (A) a polyether ether ketone compound which has a maleimide group, (B) an epoxy resin, and (C) an active ester type hardening|curing agent by using It has been found that the above problems can be solved, and the present invention has been completed.

That is, the present invention includes the following.

[1] (A) a polyether ether ketone compound having a maleimide group;

(B) an epoxy resin, and

(C) A resin composition comprising an active ester-based curing agent.

[2] The resin composition according to [1], wherein the number average molecular weight of the component (A) is 10000 or less.

[3] The resin composition according to [1] or [2], wherein the component (A) has a maleimide group at the terminal.

[4] The resin composition according to any one of [1] to [3], wherein the content of the component (A) is 5% by mass or more and 60% by mass or less when the resin component in the resin composition is 100% by mass.

[5] The resin composition according to any one of [1] to [4], wherein the component (B) contains a naphthol-type epoxy resin.

[6] The resin composition according to any one of [1] to [5], wherein the component (C) is at least one selected from a dicyclopentadiene type active ester curing agent and a naphthalene type active ester curing agent.

[7] The resin composition according to any one of [1] to [6], further comprising (D) a resin having a polymerizable unsaturated group.

[8] The resin composition according to [7], wherein the component (D) is a resin containing a maleimide group and an aromatic ring.

[9] The resin composition according to any one of [1] to [8], further comprising (E) an inorganic filler.

[10] The resin composition according to [9], wherein the content of the component (E) is 40% by mass or more and 65% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[11] The resin composition according to any one of [1] to [10], which is for forming an insulating layer.

[12] The resin composition according to any one of [1] to [11], which is for forming an insulating layer for forming a conductor layer.

[13] A resin sheet comprising a support and a resin composition layer provided on the support and comprising the resin composition according to any one of [1] to [12].

[14] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [12].

[15] A semiconductor device comprising the printed wiring board according to [14].

ADVANTAGE OF THE INVENTION According to this invention, a resin composition from which a hardened|cured material with a high glass transition temperature can be obtained which is excellent in peeling strength even if a dielectric characteristic is low and surface roughness is small; a resin sheet comprising a resin composition layer comprising the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board. can provide

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below by showing embodiments and examples. However, this invention is not limited to the embodiment and illustration shown below, The range which does not deviate from the range which does not deviate from the range which does not deviate from the claim of this invention and its equivalent can be implemented by changing arbitrarily.

[resin composition]

The resin composition of the present invention contains (A) a polyether ether ketone compound having a maleimide group, (B) an epoxy resin, and (C) an active ester curing agent. According to such a resin composition, even if a dielectric characteristic is low and surface roughness is small, it is excellent in peeling strength, and hardened|cured material with a high glass transition temperature can be obtained.

The resin composition may further optionally contain optional components such as (D) a resin containing a radically polymerizable unsaturated group, (E) an inorganic filler, (F) a curing agent, (G) a curing accelerator, and (H) other additives. may contain

<(A) polyether ether ketone compound having maleimide group>

The resin composition contains, as component (A), a polyether ether ketone compound having a maleimide group. The maleimide group is represented by the following formula (A-1). By containing (A) component in a resin composition, hardened|cured material with a high glass transition temperature can be obtained.

Formula (A-1)

(A) component can use the compound which has a maleimide group and has a polyether ether ketone (PEEK) structure. It is preferable to have 1 or more per (A) component molecule, It is more preferable to have 2 or more, It is preferable to have 10 or less, It is more preferable to have 5 or less, It is more preferable to have 3 or less. It is preferable to have a maleimide group at the terminal of (A) component from a viewpoint of obtaining the hardened|cured material excellent in dielectric properties, and, as for a maleimide group, it is more preferable to have a maleimide group at both terminals.

(A) Component has a polyether ether ketone structure. As the polyether ether ketone structure, it is preferable to have a structure represented by the following general formula (A-2).

Formula (A-2)

In Formula (A-2), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , and Ar ⁵ each independently represent a divalent aromatic hydrocarbon group. n represents the integer of 2-50. * indicates a bond.

An aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring. However, the aromatic hydrocarbon group does not need to be constituted of only an aromatic ring, and may contain a chain structure or an alicyclic hydrocarbon group in a part thereof, and the aromatic ring may be any one of monocyclic, polycyclic and heterocyclic rings.

Examples of the divalent aromatic hydrocarbon group include an arylene group, an aralkylene group, and a group having an arylene-alkylene-arylene structure.

As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is still more preferable. As such an arylene group, a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, etc. are mentioned, for example.

The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and still more preferably an aralkylene group having 7 to 15 carbon atoms. Examples of such an aralkylene group include a benzylene group and a group having a biphenylene-methylene structure.

Arylene in the group having an arylene-alkylene-arylene structure is the same as the above-described arylene group. As alkylene, a C1-C10 alkylene group is preferable, a C1-C6 alkylene group is more preferable, A C1-C3 alkylene group is still more preferable. As such alkylene, methylene, ethylene, propylene, etc. are mentioned, for example. Moreover, alkylene may have a substituent. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; A halogenated alkyl group etc. are mentioned, A C1-C3 alkyl group and halogenated alkyl group are preferable, a methyl group and a trifluoromethyl group are more preferable, and a methyl group is still more preferable. Specific examples of the group having such an arylene-alkylene-arylene structure include structures represented by the following formulas (1) to (2). Among them, the group represented by the general formula (1) is preferable.

Formula (1)

Formula (2)

In the formula, "*" represents a bond.

Among these, as Ar ¹ , Ar ² , Ar ⁴ , and Ar ⁵ , an arylene group or a group having an arylene-alkylene-arylene structure is preferable, an arylene group is more preferable, and a phenylene group is still more preferable. Ar ³ is preferably an arylene group or a group having an arylene-alkylene-arylene structure, more preferably a group having an arylene-alkylene-arylene structure, and a phenylene-dimethylmethylene-phenylene structure A group (group represented by the general formula (1)) is more preferable.

n represents the integer of 2-50, Preferably the integer of 3-40 is shown, More preferably, the integer of 4-30 is shown, More preferably, the integer of 5-20 is shown.

Specific examples of the structure represented by the formula (A-2) include, but are not limited to, structures represented by the following formulas (A1) to (A2) (in the formula, * is a bond represents).

Formula (A1)

Formula (A2)

n1 and n2 are the same as n in the formula (A-2).

(A) As a component, it is preferable that it is a compound represented by following formula (A-3).

Formula (A-3)

In the formula, D ¹ and D ² each independently represent a single bond or a divalent linking group. Ar ¹¹ , Ar ¹² , Ar ¹⁴ , and Ar ¹⁵ are each independently the same as Ar ¹ , Ar ² , Ar ⁴ , and Ar ⁵ in Formula (A-2). Ar ¹³ is each independently the same as Ar ³ in formula (A-2). m is the same as n in the formula (A-2).

D ¹ and D ² each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and a group in which a plurality of these are linked. The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group.

As a divalent aliphatic hydrocarbon group, a C1-C18 linear or branched alkylene group, a C2-C18 linear or branched alkenylene group, etc. are mentioned, for example. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. As a C2-C18 linear or branched alkenylene group, a vinylene group, 1-methylvinylene group, propenylene group, 1-butenylene group, 2-butenylene group etc. are mentioned, for example.

Examples of the divalent alicyclic hydrocarbon group include a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, for example, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, Cycloalkylene groups (including a cycloalkylidene group), such as a 1,2-cyclohexylene group, a 1, 3- cyclohexylene group, a 1, 4- cyclohexylene group, and a cyclohexylidene group, etc. are mentioned.

As a divalent aromatic hydrocarbon group, a C6-C14 arylene group etc. are mentioned, for example, For example, a 1,2-phenylene group, a 1, 4- phenylene group, a 1, 3- phenylene group, 4 ,4'-biphenylene group, 3,3'-biphenylene group, 2,6-naphthylene group, 2,7-naphthylene group, 1,8-naphthylene group, anthracenylene group, etc. are mentioned.

An aromatic heterocycle and a non-aromatic heterocycle are contained in the heterocycle constituting the divalent heterocyclic group. Examples of the heterocycle include 3- to 10-membered rings having a carbon atom and at least one heteroatom in atoms constituting the ring, condensed rings thereof, and the like. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example. A 3-10 membered ring is preferable and, as for a heterocyclic ring, a 4-6 membered ring is more preferable. As a heterocyclic ring which comprises a bivalent heterocyclic group, For example, 3-membered rings, such as an oxirane ring; 4-membered rings, such as an oxetane ring; Furan ring, tetrahydrofuran ring, oxazole ring, isoxazole ring, γ-butyrolactone ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole ring , 5-membered rings such as triazole rings; 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring, 4-oxo-4H-thiopyran ring, isocyanuric ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring , 6-membered rings such as piperazine ring; bridging rings such as 3-oxatricyclo[4.3.1.1 ^4,8 ]undecan-2-one ring and 3-oxatricyclo[4.2.1.0 ^4,8 ]nonan-2-one ring; Benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, isochroman ring, benzothiophene ring, indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring Condensed rings, such as a purine ring, etc. are mentioned. The divalent heterocyclic group is a group obtained by removing two hydrogen atoms from the structural formula of the heterocycle.

Among them, as D ¹ and D ² , it is preferable to represent a divalent aromatic hydrocarbon group from the viewpoint of significantly obtaining the effects of the present invention, more preferably to represent an arylene group having 6 to 16 carbon atoms, a 1,2-phenylene group; 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 3,3'-biphenylene group, 2,6-naphthylene group, 2,7-naphthylene group, 1, It is more preferable to represent an 8-naphthylene group or an anthracenylene group, and it is particularly preferable to represent a 1,2-phenylene group, a 1,4-phenylene group, or a 1,3-phenylene group.

(A) Although the following are mentioned as a specific example of a component, this invention is not limited to this. In the following formula, na and nb each independently represent an integer of 2 to 50.

Formula (Ai)

Formula (Aii)

(A) As a component, a commercially available thing may be used and what was synthesize|combined by a well-known method may be used for it. (A) As a synthesis|combining method of a component, it can synthesize|combine using the synthesis method described in Polymer 1989, p.978, for example. (A) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(A) The weight average molecular weight of the component is preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to copper foil. Preferably it is 10000 or less, More preferably, it is 7500 or less, More preferably, it is 5000 or less.

The weight average molecular weight of resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

(A) The number average molecular weight of the component is preferably 1000 or more, more preferably 1200 or more, still more preferably 1400 or more, from the viewpoint of obtaining a cured product having low dielectric properties and excellent adhesion to copper foil. Preferably it is 10000 or less, More preferably, it is 7500 or less, More preferably, it is 5000 or less.

The number average molecular weight of resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

(A) As content of component, when the non-volatile component in a resin composition is 100 mass % from a viewpoint of obtaining the hardened|cured material which has low dielectric characteristic and is excellent in adhesiveness with copper foil, Preferably it is 1 mass % or more, More preferably Preferably it is 3 mass % or more, More preferably, it is 5 mass % or more, Preferably it is 25 mass % or less, More preferably, it is 20 mass % or less, More preferably, it is 15 mass % or less.

In addition, in this invention, unless otherwise indicated, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass %.

(A) As content of component, when the resin component in a resin composition is 100 mass % from a viewpoint of obtaining the hardened|cured material which has low dielectric characteristic and is excellent in adhesiveness with copper foil, Preferably it is 5 mass % or more, More preferably is 10% by mass or more, more preferably 15% by mass or more, preferably 60% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less. . A resin component means the component except the (E) inorganic filler among the non-volatile components in a resin composition.

<(B) Epoxy resin>

A resin composition contains an epoxy resin as (B) component. (B) By containing an epoxy resin in a resin composition, a dielectric property is low and the hardened|cured material excellent in peeling strength can be obtained.

(B) As a component, a bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol is, for example, Type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclo A hexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, etc. are mentioned. Especially, as (B) component, a naphthol-type epoxy resin is preferable from a viewpoint of acquiring the effect of this invention remarkably.

It is preferable that the resin composition contains the epoxy resin which has two or more epoxy groups in 1 molecule as (B) component. From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the nonvolatile component of component (B) is preferably 20% by mass or more, more preferably Preferably it is 30 mass % or more, Especially preferably, it is 40 mass % or more.

In the epoxy resin, a liquid epoxy resin at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20°C (hereinafter sometimes referred to as “solid epoxy resin”) are included. have. The resin composition may contain, as component (B), only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin, but the desired effect of this invention From the viewpoint of significantly obtaining a, it is preferable to include only a solid epoxy resin.

As a solid epoxy resin, the solid epoxy resin which has 3 or more epoxy groups in 1 molecule is preferable, and the aromatic solid epoxy resin which has 3 or more epoxy groups in 1 molecule is more preferable.

Examples of the solid-state epoxy resin include a bixylenol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a bi A phenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin are preferable, and a naphthol type epoxy resin is more preferable.

As a specific example of a solid-state epoxy resin, "HP4032H" by DIC (naphthalene type epoxy resin); "HP-4700", "HP-4710" by DIC company (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC (cresol novolak-type epoxy resin); "N-695" by DIC (cresol novolak type epoxy resin); "HP-7200", "HP-7200HH", and "HP-7200H" by DIC (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" by DIC company (naphthylene ether type epoxy resin); "EPPN-502H" by a Nippon Kayaku company (trisphenol type epoxy resin); "NC7000L" by a Nippon Kayaku company (naphthol novolak-type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) by the Nippon Kayaku company; "ESN475V" (naphthol type epoxy resin) by the Nitetsu Chemical & Materials company; "ESN485" (naphthol novolak-type epoxy resin) by the Nitetsu Chemical & Materials company; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) by a Mitsubishi Chemical company; "YX4000HK" by a Mitsubishi Chemical company (bixylenol type epoxy resin); "YX8800" (anthracene type epoxy resin) by a Mitsubishi Chemical company; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" by a Mitsubishi Chemical company (bisphenol AF type|mold epoxy resin); "YL7800" by Mitsubishi Chemical (fluorene type epoxy resin); "jER1010" by Mitsubishi Chemical (solid bisphenol A epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) by a Mitsubishi Chemical company, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As a liquid epoxy resin, the liquid epoxy resin which has two or more epoxy groups in 1 molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin , an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure, more preferably a naphthalene type epoxy resin do.

As a specific example of a liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" naphthalene type epoxy resin by DIC Corporation); "828US", "jER828EL", "825", "Epicoto 828EL" by Mitsubishi Chemical Corporation (bisphenol A epoxy resin); "jER807", "1750" by Mitsubishi Chemical Corporation (bisphenol F-type epoxy resin); "jER152" by Mitsubishi Chemical (phenol novolak type epoxy resin); "630" and "630LSD" by Mitsubishi Chemical (glycidylamine type epoxy resin); "ZX1059" (mixed product of a bisphenol A epoxy resin and a bisphenol F type epoxy resin) by the Nitetsu Chemical & Materials company; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd.; "Celoxide 2021P" by Daicel (alicyclic epoxy resin which has ester skeleton); "PB-3600" by Daicel (epoxy resin which has a butadiene structure); "ZX1658", "ZX1658GS" (liquid 1, 4- glycidyl cyclohexane type epoxy resin), etc. by the Nitetsu Chemical & Materials company are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) When a liquid epoxy resin and a solid epoxy resin are used in combination as a component, their ratio (liquid epoxy resin:solid epoxy resin) is a mass ratio, preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, particularly preferably 1:2 to 1:10. When the amount ratio of the liquid epoxy resin and the solid epoxy resin is within this range, the desired effect of the present invention can be significantly obtained. Moreover, when using in the form of a resin sheet normally, moderate adhesiveness is formed. Moreover, when using in the form of a resin sheet normally, sufficient flexibility can be acquired and handleability improves. Moreover, usually, the hardened|cured material which has sufficient breaking strength can be obtained.

(B) The epoxy equivalent of component becomes like this. Preferably it is 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., more preferably 80 g/eq. to 2000 g/eq., even more preferably 110 g/eq. to 1000 g/eq. By being set to this range, the crosslinking density of the hardened|cured material of a resin composition layer becomes enough, and the insulating layer with a small surface roughness can be formed. Epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JISK7236.

The weight average molecular weight (Mw) of the component (B) is preferably 100 to 5000, more preferably 200 to 3000, still more preferably 250 to 1500 from the viewpoint of significantly obtaining the desired effect of the present invention.

(B) The content of the component, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and good insulation reliability, when the nonvolatile component in the resin composition is 100 mass%, preferably 5 mass% or more, more preferably is 10 mass % or more, More preferably, 15 mass % or more. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less from the viewpoint of significantly obtaining the desired effect of the present invention.

As the content of the component (B), from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and good insulation reliability, when the resin component in the resin composition is 100% by mass, preferably 20% by mass or more, more preferably 25 mass % or more, More preferably, it is 30 mass % or more, Preferably it is 50 mass % or less, More preferably, it is 45 mass % or less, More preferably, it is 40 mass % or less.

<(C) Active ester-based curing agent>

The resin composition contains (C) an active ester curing agent. By using an active ester type hardening|curing agent, a dielectric property can be improved and it becomes excellent in peeling strength. (C) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) As the active ester curing agent, generally two ester groups with high reactive activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, per molecule The compounds having the above are preferably used. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Specifically, as component (C), a dicyclopentadiene type active ester curing agent, a naphthalene type active ester curing agent, an active ester curing agent containing an acetylated product of phenol novolac, and a benzoyl product of phenol novolac. An active ester type hardening|curing agent etc. are mentioned. A naphthalene type active ester type hardening|curing agent contains a naphthalene structure. Among them, as component (C), at least one selected from a dicyclopentadiene type active ester curing agent and a naphthalene type active ester curing agent is more preferable, and a naphthalene type active ester curing agent is still more preferable. As the dicyclopentadiene type active ester curing agent, an active ester curing agent having a dicyclopentadiene type diphenol structure is preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

(C) Commercially available active ester curing agents are active ester curing agents containing a dicyclopentadiene type diphenol structure, such as “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC” -8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC); As a naphthalene-type active ester curing agent, "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150- 62T" (manufactured by DIC Corporation), and "PC1300-02-65T" (manufactured by Air Water Corporation); As an active ester curing agent containing an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical); "YLH1026" (made by Mitsubishi Chemical) as an active ester type hardening|curing agent containing the benzoyl product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical) as an active ester curing agent that is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is a benzoyl product of phenol novolac; "EXB-8500-65T" (made by DIC); and the like.

(C) The active ester group equivalent of the active ester curing agent is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., more preferably 100 g/eq. to 300 g/eq. The active ester group equivalent is the mass of the active ester-based curing agent containing 1 equivalent of the active ester group.

The amount ratio of (B) epoxy resin and (C) active ester curing agent is [total number of active groups in active ester curing agent] / [total number of epoxy groups in epoxy resin], preferably 0.01 or more, more preferably Preferably it is 0.3 or more, More preferably, it is 0.5 or more, Preferably it is 5 or less, More preferably, it is 3 or less, More preferably, it is 2 or less. Here, "the number of epoxy groups of an epoxy resin" is the value which summed up all the values obtained by dividing the mass of the nonvolatile component of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of an active ester-type hardening|curing agent" is the total value of all the values obtained by dividing the mass of the non-volatile components of the active ester-based curing agent present in the resin composition by the equivalent of active ester groups. By making the ratio between the epoxy resin and the active ester curing agent within such a range, it becomes possible to significantly obtain the effects of the present invention.

(C) Content of an active ester type hardening|curing agent, while making a dielectric property low, from a viewpoint of obtaining the hardened|cured material excellent in peeling strength, when the nonvolatile component in a resin composition is 100 mass %, Preferably it is 1 mass % or more, more preferably 5 mass % or more, still more preferably 10 mass % or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.

(C) As content of an active ester type hardening|curing agent, when a resin component in a resin composition is 100 mass % from a viewpoint of obtaining the hardened|cured material which can make dielectric properties low and is excellent in peeling strength, Preferably it is 10 mass % More preferably, it is 20 mass % or more, More preferably, it is 25 mass % or more, Preferably it is 50 mass % or less, More preferably, it is 45 mass % or less, More preferably, it is 40 mass % or less.

<(D) Resin containing a radically polymerizable unsaturated group>

The resin composition may contain resin containing (D) radically polymerizable unsaturated group as arbitrary components other than the component mentioned above. (D) By containing resin containing a radically polymerizable unsaturated group in a resin composition, the hardened|cured material excellent in a peeling strength with a low dielectric characteristic can be obtained. (D) Component, the thing corresponding to (A) component - (C)component is excluded.

(D) The radically polymerizable unsaturated group which component contains represents the group containing the unsaturated bond which shows radically polymerizable. As this radically polymerizable unsaturated group, the group containing an ethylenic double bond is mentioned, for example. (D) component containing such a radically polymerizable unsaturated group can generate|occur|produce radical polymerization with a heat|fever or an active energy ray, and can harden a resin composition.

Examples of the radical polymerizable unsaturated group include a maleimide group, a vinyl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, a maleoyl group, a benzocyclobutene group, and an allyl group. . Especially, as (D)component, a maleimide group is preferable from a viewpoint of acquiring the effect of this invention remarkably. (D) The number of the radically polymerizable unsaturated groups which a component contains is 1 or more normally, Preferably it is 2 or more. (D) When a component contains two or more radically polymerizable unsaturated groups, these two or more radically polymerizable unsaturated groups may be same or different.

(D) As a component, it is preferable to use resin which contains an aromatic ring in a molecule|numerator. Therefore, as for (D) component, resin containing an aromatic ring and a radically polymerizable unsaturated group is preferable. (D) An aromatic carbocyclic ring may be sufficient as the aromatic ring contained in component, and an aromatic heterocyclic ring may be sufficient as it. In addition, the aromatic ring may be a monocyclic aromatic ring, or may be a condensed aromatic ring obtained by condensing two or more monocyclic aromatic rings, or may be a condensed aromatic ring obtained by condensing one or more monocyclic aromatic rings to one or more monocyclic aromatic rings. Directional rings are also good. As these aromatic rings, For example, monocyclic aromatic rings, such as a benzene ring and a pyridine ring; Condensed aromatic rings, such as an indan ring, a fluorene ring, and a naphthalene ring; can be heard Especially, as for an aromatic ring, an aromatic carbocyclic ring is preferable. The number of carbon atoms of the aromatic carbocyclic ring is preferably 6 or more and 10 or less.

(D) A substituent may couple|bond with the aromatic ring contained in component. One may be sufficient as the number of the substituent couple|bonded with one aromatic ring, and 2 or more may be sufficient as it. When the number of substituents is two or more, these two or more substituents may be same or different.

Examples of the substituent include an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group.

The number of carbon atoms in the alkyl group is preferably 1 to 10. As an alkyl group, a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group, etc. are mentioned, for example.

The number of carbon atoms in the alkyloxy group is preferably 1 to 10. As an alkyloxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

The number of carbon atoms in the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group.

The number of carbon atoms in the aryl group is preferably 6 to 10. As an aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example.

The number of carbon atoms in the aryloxy group is preferably 6 to 10. As an aryloxy group, a phenyloxy group, a naphthyloxy group, etc. are mentioned, for example.

The number of carbon atoms in the arylthio group is preferably 6 to 10. As an arylthio group, a phenylthio group, a naphthylthio group, etc. are mentioned, for example.

The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

As a halogen atom, a fluorine atom, a chlorine atom, an iodine atom, etc. are mentioned, for example.

Especially, as for the aromatic ring which component (D) contains, it is preferable that the substituent is not couple|bonded, or that the alkyl group has couple|bonded.

(D) The number of the aromatic rings contained in a component is 1 or more normally, Preferably it is 2 or more. (D) When a component contains two or more aromatic rings, these two or more aromatic rings may be same or different.

(D) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) One preferred embodiment of the component is a resin containing a maleimide group. It is preferable that resin containing a maleimide group contains an aromatic ring further. Since resin containing a maleimide group is resin which belongs to (D) component, the thing corresponding to (A) component is excluded. Resin containing a maleimide group may be used individually by 1 type, and may be used in combination of 2 or more type.

As resin containing a maleimide group,

(D-1) a maleimide compound containing an aliphatic group having 5 or more carbon atoms directly bonded to the nitrogen atom of the maleimide group;

(D-2) a maleimide compound having an aromatic ring directly bonded to the nitrogen atom of the maleimide group, and

(D-3) a maleimide compound comprising a trimethylindane skeleton;

It is preferable that at least one selected from

Here, the term "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aliphatic group having 5 or more carbon atoms in the component (D-1), and in the component (D-2), maleimide It means that there is no other group between the nitrogen atom of the imide and the aromatic ring.

(D-1) Component is a maleimide compound containing the C5 or more aliphatic group directly couple|bonded with the nitrogen atom of maleimide. (D-1) component, for example, an aliphatic amine compound (diamine compound having a dimer acid skeleton, etc.), maleic anhydride, and, if necessary, a component containing tetracarboxylic dianhydride can be obtained by imidation reaction. have.

Examples of the aliphatic group having 5 or more carbon atoms include an alkyl group, an alkylene group, and an alkenylene group.

The number of carbon atoms in the alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Any of linear, branched, and cyclic|annular form may be sufficient as this alkyl group, and linear is especially preferable. As such an alkyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group etc. are mentioned, for example. The C5 or more alkyl group may have as a substituent of the C5 or more alkylene group. The alkyl group having 5 or more carbon atoms may be a part of an alkenyl group or a part of an alkapolyenyl group (the number of double bonds is preferably 2).

The number of carbon atoms in the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Linear, branched, or cyclic any may be sufficient as this alkylene group, and linear is especially preferable. Here, the cyclic alkylene group is a concept that includes both a case consisting of a cyclic alkylene group and a case containing both a linear alkylene group and a cyclic alkylene group. Examples of such an alkylene group include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, and a hexatriacone group. The group which has a tylene group, the group which has an octylene-cyclohexylene structure, the group which has an octylene-cyclohexylene-octylene structure, and a propylene-cyclohexylene-octylene structure, etc. are mentioned. The alkylene group having 5 or more carbon atoms may be a part of an alkenylene group or a part of an alkapolyenylene group (the number of double bonds is preferably 2).

The number of carbon atoms in the alkenylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Linear, branched, or cyclic any may be sufficient as this alkenylene group, and linear is especially preferable. Here, the cyclic alkenylene group is a concept that includes both a case consisting of only a cyclic alkenylene group and a case containing both a linear alkenylene group and a cyclic alkenylene group. As such an alkenylene group, for example, pentynylene group, hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecinylene group, dodecinylene group, tridecinylene group, hepta Decynylene group, hexatriacontinylene group, octynylene-cyclohexynylene group having a structure, octynylene-cyclohexynylene-octynylene structure having a group, propynylene-cyclohexynylene-octynylene structure having a structure and the like.

(D-1) As a component, the compound represented by the following general formula (D-1-1) is preferable.

Formula (D-1-1)

In the general formula (D-1-1), M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. The number of carbon atoms in the divalent aliphatic group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Linear, branched, or cyclic any may be sufficient as this aliphatic group, and linear is especially preferable. Here, the cyclic aliphatic group is a concept that includes both a case composed of only a cyclic aliphatic group and a case containing both a linear aliphatic group and a cyclic aliphatic group. Examples of the divalent aliphatic group include an alkylene group, an alkenylene group, and an alkapolyenylene group (more preferably the number of double bonds is 2). The alkylene group and the alkenylene group are as described above.

Examples of the substituent for M include a halogen atom, -OH, -OC _1-10 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _2-30 alkenyl group, C _2-30 alkynyl group, C _6-10 aryl group, -NH ₂ , -CN, -C(O)OC _1-10 alkyl group, -COOH, -C(O)H, -NO ₂ , and the like. Here, the term “C _xy ” (x and y are positive integers, satisfying x<y) indicates that the number of carbon atoms in the organic group described immediately after this term is x to y. For example, the expression "C _1-10 alkyl group" represents an alkyl group having 1 to 10 carbon atoms. These substituents may combine with each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. The substituent is preferably an alkyl group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C(=O)-, -C(=O)-O-, -NR ⁰ -(R ⁰ is a hydrogen atom, a carbon atom 1 to 3 alkyl group), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and two or more kinds of divalent groups The group which consists of a combination of groups, etc. are mentioned. A group consisting of a combination of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and two or more types of divalent groups has the number of carbon atoms You may have 5 or more alkyl groups as a substituent. The divalent group derived from phthalimide represents a divalent group derived from phthalimide, and is specifically a group represented by the general formula (D-1-2). The divalent group derived from pyromellitic acid diimide represents a divalent group derived from pyromellitic acid diimide, and is specifically a group represented by general formula (D-1-3). In the formula, "*" represents a bond.

General formula (D-1-2)

General formula (D-1-3)

The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, particularly preferably an alkylene group having 1 to 40 carbon atoms. do. Any of linear, branched, and cyclic|annular form may be sufficient as this alkylene group. Examples of such an alkylene group include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, and a tridecylene group. , a heptadecylene group, a hexatriacontylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a propylene-cyclohexylene-octylene structure, etc. can be heard

The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 50 carbon atoms, more preferably an alkenylene group having 2 to 45 carbon atoms, particularly preferably an alkenylene group having 2 to 40 carbon atoms. do. The alkenylene group may be linear, branched or cyclic. Examples of the alkenylene group include a methylethylenylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group.

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 50 carbon atoms, more preferably an alkynylene group having 2 to 45 carbon atoms, particularly preferably an alkynylene group having 2 to 40 carbon atoms. do. Any of linear, branched, and cyclic|annular form may be sufficient as this alkynylene group. Examples of the alkynylene group include a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptynylene group, and an octynylene group.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms. and an arylene group having 6 to 10 carbon atoms is more preferable. As an arylene group, a phenylene group, a naphthylene group, anthracenylene group, etc. are mentioned, for example.

The alkylene group, alkenylene group, alkynylene group, and arylene group which are divalent coupling groups in L may have a substituent. As a substituent, it is the same as the substituent of M in general formula (B2-1-1), Preferably it is a C5 or more alkyl group.

Examples of the group consisting of a combination of two or more divalent groups in L include a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group consisting of a combination of a phthalimide-derived divalent group, an oxygen atom, an arylene group, and an alkylene group; a divalent group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; and the like. The group which consists of a combination of 2 or more types of divalent groups may form rings, such as a condensed ring, by combining each group. Moreover, the repeating unit of 1-10 repeating units may be sufficient as the group which consists of a combination of 2 or more types of divalent groups.

Among them, as L in the general formula (D-1-1), an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, an alkylene group having 1 to 50 carbon atoms which may have a substituent, and carbon It is preferable that the number of atoms is a divalent group composed of an alkyl group having 5 or more atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a combination of two or more of these groups. Among them, as L, an alkylene group; a divalent group having the structure of an alkylene group-phthalimide-derived divalent group-oxygen atom- a phthalimide-derived divalent group; a divalent group having a structure of an alkylene group-phthalimide-derived divalent group-oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-phthalimide-derived divalent group; a divalent group having a structure of a divalent group derived from alkylene-pyromellitic diimide; a divalent group having a structure of alkynylene group-phthalimide-derived divalent group-oxygen atom-phthalimide-derived divalent group; a divalent group having a structure of alkynylene group-phthalimide-derived divalent group-oxygen atom-arylene group-alkynylene group-arylene group-oxygen atom-phthalimide-derived divalent group; A divalent group having a structure of a divalent group derived from alkynylene-pyromellitic diimide is more preferable.

It is preferable that maleimide resin represented by general formula (D-1-1) is maleimide resin represented by general formula (D-1-4).

General formula (D-1-4)

In the general formula (D-1-4), M ¹ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and Z each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent An aliphatic group or a divalent group having an aromatic ring which may have a substituent is shown. t represents the integer of 1-10.

M ¹ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ¹ is the same as M in general formula (D-1-1).

Z each independently represents a divalent group having an aromatic ring which may have a substituent or a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. Examples of the divalent aliphatic group in Z include an alkylene group, an alkenylene group, and an alkapolyenylene group (more preferably, the number of double bonds is 2). The divalent aliphatic group may be any of chain, branched, and cyclic, and among these, a cyclic, that is, a cyclic divalent aliphatic group having 5 or more carbon atoms which may have a substituent is preferable.

The number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure. have.

The number of carbon atoms in the alkenylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Linear, branched, or cyclic any may be sufficient as this alkenylene group, and linear is especially preferable. Here, the cyclic alkenylene group is a concept that includes both a case consisting of only a cyclic alkenylene group and a case containing both a linear alkenylene group and a cyclic alkenylene group. As such an alkenylene group, for example, pentynylene group, hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecinylene group, dodecinylene group, tridecinylene group, hepta Decynylene group, hexatriacontinylene group, octynylene-cyclohexynylene group having a structure, octynylene-cyclohexynylene-octynylene structure having a group, propynylene-cyclohexynylene-octynylene structure having a structure and the like.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and an aromatic heterocycle, A benzene ring, a phthalimide ring, and a pyromellitic acid diimide ring are preferable. That is, the divalent group having an aromatic ring is a divalent group having a benzene ring which may have a substituent, a divalent group having an optionally substituted phthalimide ring, and a pyromellitic acid diimide ring which may have a substituent. A divalent group having Examples of the divalent group having an aromatic ring include a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a group consisting of a combination of a phthalimide-derived divalent group, an oxygen atom, an arylene group, and an alkylene group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group derived from pyromellitic acid diimide; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; and the like. The arylene group is the same as the arylene group in the divalent linking group represented by L in the general formula (D-1-1).

The divalent group which has an alkylene group and an aromatic ring which Z represents may have a substituent. As a substituent, it is the same as the substituent which M in general formula (D-1-1) may have.

Specific examples of the group represented by Z include the following groups. In the formula, "*" represents a bond.

It is preferable that the compound represented by the general formula (D-1-1) is any one of the compound represented by the general formula (D-1-5) and the compound represented by the general formula (D-1-6). .

General formula (D-1-5)

General formula (D-1-6)

In the general formula (D-1-5), M ² and M ³ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and R ⁴⁰ each independently represents an oxygen atom, an arylene group, or an alkyl group. It represents a divalent group consisting of a ren group or a combination of two or more of these groups. t1 represents the integer of 1-10.

In the general formula (D-1-6), M ⁴ , M ⁶ and M ⁷ each independently represents an aliphatic group having 5 or more carbon atoms which may have a substituent, and M ⁵ is each independently an aromatic ring which may have a substituent represents a divalent group having a , and R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

M ² and M ³ each independently represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ² and M ³ are the same as the divalent aliphatic group in which the number of carbon atoms represented by M in the general formula (D-1-1) is 5 or more, and preferably a hexatriacontinylene group or a hexatriacontylene group.

R ⁴⁰ each independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more kinds of divalent groups thereof. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (D-1-1). As R ⁴⁰ , it is preferable that it is a group consisting of a combination of two or more types of divalent groups or an oxygen atom.

As a group which consists of a combination of 2 or more types of divalent group in R< ⁴⁰ >, the combination of an oxygen atom, an arylene group, and an alkylene group is mentioned. The following groups are mentioned as a specific example of the group which consists of a combination of 2 or more types of divalent groups. In the formula, "*" represents a bond.

M ⁴ , M ⁶ and M ⁷ each independently represent an aliphatic group having 5 or more carbon atoms which may have a substituent. M ⁴ , M ⁶ and M ⁷ are the same as an aliphatic group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (D-1-1), and a hexylene group, a heptylene group, an octylene group, and a nonylene group , a decylene group is preferable, and an octylene group is more preferable.

M ⁵ each independently represents a divalent group having an aromatic ring which may have a substituent. M ⁵ is the same as the divalent group having an aromatic ring which may have a substituent represented by Z in the general formula (D-1-4), and is a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide. ; A group consisting of a combination of a divalent group derived from phthalimide and an alkylene group is preferable, and a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic diimide is more preferable. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (D-1-1).

Specific examples of the group represented by M ⁵ include the following groups. In the formula, "*" represents a bond.

R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. R ⁴¹ and R ⁴² are the same as the above-described alkyl group having 5 or more carbon atoms, preferably a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group, and more preferably a hexyl group or an octyl group.

u1 and u2 each independently represent the integer of 1-15, The integer of 1-10 is preferable.

(D-1) As a specific example of a component, the compound of the following (D-i) - (D-iii) is mentioned, It is not limited to these specific examples. In the formula, v represents an integer from 1 to 10.

Formula (D-i)

Formula (D-ii)

Formula (D-iii)

(D-1) Specific examples of the component include "BMI1500" (compound of formula (Di)) manufactured by Designer Molecules, "BMI1700" (compound of formula (D-ii)), "BMI689" (formula (D-) compound of iii)), and the like.

(D-1) The weight average molecular weight (Mw) of a component becomes like this. Preferably it is 150-5000, More preferably, it is 300-2500.

(D-1) The maleimide group equivalent of the component is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq., more preferably 150 g/eq. to 500 g/eq. Maleimide group equivalent is the mass of component (D-1) containing 1 equivalent of maleimide group.

(D-2) A component is a maleimide compound which has an aromatic ring directly couple|bonded with the nitrogen atom of maleimide. (D-2) A component can be obtained by making imidation reaction of the component containing an aromatic amine compound (aromatic diamine compound etc.) and maleic anhydride, for example.

The aromatic ring may be a carbocyclic ring or a heterocyclic ring. Examples of the aromatic ring include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, pyra monocyclic aromatic rings, such as a true ring; Naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzoimidazole ring, indazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, quinoline ring , a condensed ring in which two or more monocyclic aromatic rings such as an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring and a phthalazine ring are condensed; Condensed rings etc. which 1 or more monocyclic non-aromatic rings condensed to 1 or more monocyclic aromatic rings, such as an indan ring, a fluorene ring, and a tetralin ring, are mentioned. Especially, as an aromatic ring, a monocyclic aromatic ring is preferable and a benzene ring is more preferable.

(D-2) As a component, the compound represented by following formula (D-2-1) is preferable.

Formula (D-2-1)

In the formula, each R ^c independently represents a substituent; X ^c is each independently a single bond, an alkylene group, an alkenylene group, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, -COO- , or -OCO- (preferably a single bond or an alkylene group); Z ^c is each independently a non-aromatic ring which may have a substituent, or an aromatic ring which may have a substituent (preferably an aromatic ring which may have a substituent, particularly preferably a benzene ring which may have a substituent) indicate; s represents an integer of 1 or more (preferably an integer from 1 to 100, more preferably an integer from 1 to 50, still more preferably an integer from 1 to 20); t1 each independently represents 0 or an integer of 1 or more; u each independently represents an integer of 0 to 2 (preferably 0).], particularly preferably, formulas (D-2-2) to (D-2-5). )to be:

Formula (D-2-2)

Formula (D-2-3)

Formula (D-2-4)

Formula (D-2-5)

In the formula, R ^c1 , R ^c2 and R ^c3 each independently represent an alkyl group; X ^c1 and X ^c2 each independently represent a single bond or an alkylene group; s represents an integer of 1 or more (preferably an integer from 1 to 100, more preferably an integer from 1 to 50, still more preferably an integer from 1 to 20); t' represents an integer of 1 to 5; v1, v2, and v3 each independently represent the integer of 0-2 (preferably 0). In addition, the s unit, the t unit, the t' unit, the v unit, the v1 unit, the v2 unit, and the v3 unit may be the same or different for each unit, respectively.

Moreover, as another embodiment, it is preferable that component (D-2) has a structure represented, for example by following formula (D-2-6).

Formula (D-2-6)

In the formula, R ³¹ and R ³⁶ represent a maleimide group, R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and D each independently represents a divalent aromatic group. . m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

R ³² , R ³³ , R ³⁴ and R ³⁵ in the formula (D-2-6) each independently represent a hydrogen atom, an alkyl group, or an aryl group, and a hydrogen atom is preferable.

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is still more preferable. The alkyl group may be linear, branched, or cyclic. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. A monocyclic ring may be sufficient as an aryl group, and a condensed ring may be sufficient as it. As such an aryl group, a phenyl group, a naphthyl group, anthracenyl group etc. are mentioned, for example.

The alkyl group and the aryl group may have a substituent. There is no restriction|limiting in particular as a substituent, For example, a halogen atom, -OH, -OC _1-6 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 aryl group, -NH ₂ , -CN, -C(O)OC _1-10 alkyl group, -COOH, -C(O)H, -NO ₂ etc. are mentioned. Here, the term "C _pq " (p and q are positive integers and satisfy p < q) indicates that the number of carbon atoms in the organic group described immediately after this term is p to q. For example, the expression "C _1-10 alkyl group" represents an alkyl group having 1 to 10 carbon atoms. These substituents may combine with each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.

The above-mentioned substituent may further have a substituent (Hereinafter, it may be called "secondary substituent."). As a secondary substituent, you may use the thing similar to the above-mentioned substituent unless otherwise stated.

D in the general formula (D-2-6) represents a divalent aromatic group. As a divalent aromatic group, a phenylene group, a naphthylene group, anthracenylene, an aralkyl group, a biphenylene group, a biphenyl aralkyl group etc. are mentioned, for example, Among these, a biphenylene group and a biphenyl aralkyl group preferable, and a biphenylene group is more preferable. The divalent aromatic group may have a substituent. The substituent is the same as the substituent which the alkyl group represented by R ³² in the formula (D-2-6) may have.

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, still more preferably 1 to 2, and still more preferably 1.

a represents the integer of 1-100, Preferably it is 1-50, More preferably, it is 1-20, More preferably, it is 1-5.

(D-2) As a component, resin represented by general formula (D-2-7) is preferable.

Formula (D-2-7)

In the formula, R ³⁷ and R ³⁸ represent a maleimide group. a1 represents the integer of 1-100.

a1 is the same as a in formula (D-2-6), and a preferable range is also the same.

(D-2) As a commercial item of a component, For example, "MIR-3000-70MT" by a Nippon Kayaku company; "BMI-50P" by Keii Kasei Corporation; "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-4000", "BMI-5100" manufactured by Yamato Kaseiko Co., Ltd.; "BMI-4,4'-BPE" by Keii Kasei Corporation, "BMI-70", "BMI-80" by Keii Kasei Corporation, etc. are mentioned.

(D-2) The weight average molecular weight (Mw) of a component becomes like this. Preferably it is 150-5000, More preferably, it is 300-2500.

(D-2) The functional group equivalent of the maleimide group of the component becomes like this. Preferably it is 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq. more preferably 150 g/eq. to 500 g/eq., particularly preferably 200 g/eq. to 300 g/eq.

(D-3) A component is a maleimide compound containing trimethylindane skeleton. The trimethylindane skeleton represents a skeleton represented by the following formula (D-3-1).

Formula (D-3-1)

A substituent may couple|bond with the benzene ring which trimethylindane skeleton contains. Examples of the substituent include an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cycloalkyl group, a halogen atom, a hydroxyl group, and a mercapto group.

The number of carbon atoms in the alkyl group is preferably 1 to 10. As an alkyl group, a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group, etc. are mentioned, for example.

The number of carbon atoms in the alkyloxy group is preferably 1 to 10. As an alkyloxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

The number of carbon atoms in the alkylthio group is preferably 1 to 10. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group.

The number of carbon atoms in the aryl group is preferably 6 to 10. As an aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example.

The number of carbon atoms in the aryloxy group is preferably 6 to 10. As an aryloxy group, a phenyloxy group, a naphthyloxy group, etc. are mentioned, for example.

The number of carbon atoms in the arylthio group is preferably 6 to 10. As an arylthio group, a phenylthio group, a naphthylthio group, etc. are mentioned, for example.

The number of carbon atoms in the cycloalkyl group is preferably 3 to 10. As a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group etc. are mentioned, for example.

As a halogen atom, a fluorine atom, a chlorine atom, an iodine atom, etc. are mentioned, for example.

Among the above substituents, a hydrogen atom of an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a cycloalkyl group may be substituted with a halogen atom.

The number of substituents couple|bonded with one benzene ring which trimethylindane skeleton contains may be 1, and 2 or more may be sufficient as it. The number of substituents couple|bonded with the benzene ring which trimethylindane skeleton contains is 0 or more and 3 or less normally. When the number of substituents is two or more, these two or more substituents may be same or different. Especially, it is preferable that the substituent is not couple|bonded with the benzene ring which trimethylindane frame|skeleton contains.

(D-3) The number of trimethylindane skeletons contained in 1 molecule of a component may be 1, and 2 or more may be sufficient as it. The upper limit may be, for example, 10 or less, 8 or less, 7 or less, or 6 or less.

(D-3) In addition to the trimethylindane skeleton mentioned above, it is preferable that a component further contains aromatic ring skeleton. The number of ring-constituting carbons in the aromatic ring skeleton is preferably 6 to 10. As aromatic ring skeleton, a benzene ring skeleton, a naphthalene ring skeleton, etc. are mentioned, for example. (D-3) The number of the aromatic ring skeletons contained in one molecule of the component is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, particularly preferably usually less than 3. (D-3) When a component adds and contains 2 or more aromatic ring skeleton to trimethylindane skeleton, these aromatic ring skeleton may be same or different.

A substituent may couple|bond with the aromatic ring contained in said aromatic ring skeleton. As a substituent, the substituent mentioned above as a substituent which can couple|bond with the benzene ring contained in trimethylindane skeleton contains, and a nitro group is mentioned, for example. One may be sufficient as the number of the substituent couple|bonded with one aromatic ring, and 2 or more may be sufficient as it. The number of substituents couple|bonded with an aromatic ring is 0 or more and 4 or less normally. When the number of substituents is two or more, these two or more substituents may be same or different.

(D-3) It is preferable that a component further contains a divalent aliphatic hydrocarbon group in addition to the trimethylindane skeleton mentioned above. In particular, when component (D-3) contains aromatic ring skeletons other than the benzene ring which trimethylindane skeleton contains, it is preferable that component (D-3) contains a divalent aliphatic hydrocarbon group. In this case, it is preferable that the divalent aliphatic hydrocarbon group connects between the benzene ring and aromatic ring skeleton which a trimethylindane skeleton contains. Moreover, it is preferable that the divalent aliphatic hydrocarbon group connects between aromatic ring skeletons.

The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 or more, preferably 12 or less, more preferably 8 or less, particularly preferably 5 or less. As the divalent aliphatic hydrocarbon group, an alkylene group as a saturated aliphatic hydrocarbon group is more preferable. Examples of the divalent aliphatic hydrocarbon group include a straight-chain alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; Ethylene group (-CH(CH ₃ )-), propylidene group (-CH(CH ₂ CH ₃ )-), isopropylidene group (-C(CH ₃ ) ₂ -), ethylmethylmethylene group (-C branched chain alkylene groups such as (CH ₃ )(CH ₂ CH ₃ )-) and diethylmethylene group (—C(CH ₂ CH ₃ ) ₂ -); and the like. (B2-3) When the maleimide compound having a trimethylindane skeleton contains two or more divalent aliphatic hydrocarbon groups in addition to the trimethylindane skeleton, these divalent aliphatic hydrocarbon groups may be the same or different.

(D-3) It is preferable that a component contains the structure shown by following formula (D-3-2). (D-3) The whole component may have a structure represented by general formula (D-3-2), and the part of (D-3) component may have a structure shown by general formula (D-3-2).

Formula (D-3-2)

(In the formula, Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent; R ^a1 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or a carbon atom An alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms , a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R ^a2 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms of an alkylthio group, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, represents a hydroxyl group or a mercapto group; R ^a3 each independently represents a divalent aliphatic hydrocarbon group; n _a1 represents a positive integer; n _a2 each independently represents an integer of 0 to 4; n _a3 each independently represents an integer of 0 to 3. The hydrogen atom of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R ^a1 is a halogen atom The hydrogen atom of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group of R ^a2 may be substituted with a halogen atom. n _a2 is 2 to 4 In the case of , R ^a1 may be the same or different within the same ring. When n _a3 is 2 to 3, R ^a2 may be the same or different within the same ring.)

In the formula (D-3-2), Ar ^a1 represents a divalent aromatic hydrocarbon group which may have a substituent. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 or more, preferably 20 or less, and more preferably 16 or less. Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group. Examples of the substituent that the divalent aromatic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and 6 carbon atoms. an aryl group having to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, and a mercapto group. have. The hydrogen atom of each substituent may further be substituted by the halogen atom. Moreover, as a specific example of these substituents, the same example as a substituent which can couple|bond with the benzene ring contained in trimethylindane skeleton is mentioned, for example. When the divalent aromatic hydrocarbon group has a substituent, the number of the substituents is preferably 1 to 4. When the number of substituents which the divalent aromatic hydrocarbon group has is two or more, these two or more substituents may be same or different. Among them, Ar ^a1 is preferably a divalent aromatic hydrocarbon group having no substituent.

In the formula (D-3-2), R ^a1 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, Or a mercapto group is shown. The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same examples of the substituents capable of being bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R ^a1 is more preferably at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. , an alkyl group having 1 to 4 carbon atoms is particularly preferred.

In the formula (D-3-2), R ^a2 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms; An aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercap indicates soil. The hydrogen atoms of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with a halogen atom. Specific examples of these groups include the same examples of the substituents capable of being bonded to the benzene ring contained in the trimethylindane skeleton. Among them, R ^a2 is more preferably at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. do.

In the formula (D-3-2), R ^a3 each independently represents a divalent aliphatic hydrocarbon group. The preferred range of the divalent aliphatic hydrocarbon group is as described above.

In the general formula (D-3-2), n _a1 represents a positive integer. n _a1 is preferably 1 or more, preferably 10 or less, more preferably 8 or less.

In general formula (D-3-2), n _a2 represents the integer of 0-4 each independently. n _a2 becomes like this. Preferably it is 2 or 3, More preferably, it is 2. Although a plurality of n _a2 may be different, it is preferable that they are the same. When n _a2 is 2 or more, a plurality of R ^a1s may be the same or different within the same ring.

In general formula (D-3-2), n _a3 represents the integer of 0-3 each independently. Although a plurality of n _a3 may be different, it is preferable that they are the same. n _a3 is preferably 0.

(D-3) It is especially preferable that a component contains the structure shown by following formula (D-3-3). (D-3) The whole component may have a structure represented by general formula (D-3-3), and the part of (D-3) component may have a structure shown by general formula (D-3-3).

Formula (D-3-3)

(In the formula, R ^b1 is, each independently, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, 6 to 10 carbon atoms an aryl group, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R ^b2 is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon represents an aryloxy group having 6 to 10 atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n _b1 is a positive integer n _b2 each independently represents an integer from 0 to 4 n _b3 each independently represents an integer from 0 to 3. R ^b1 represents an alkyl group, an alkyloxy group, an alkylthio group, or an aryl group , the hydrogen atom of the aryloxy group, the arylthio group, and the cycloalkyl group may be substituted with a halogen atom ^Alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, and cyclo The hydrogen atom of the alkyl group may be substituted with a halogen atom. When n _b2 is 2 to 4, R ^b1 may be the same or different within the same ring. When n _b3 is 2 to 3, R ^b2 is the same It may be the same or different within the ring.)

In the formula (D-3-3), R ^b1 , R ^b2 , n _b1 , n _b2 and n _b3 are, respectively, R ^a1 , R ^a2 , n _a1 , n _a2 in the formula (D-3-2) and n _a3 .

(B2-3) The component may further contain the structure represented by the following general formula (D-3-4).

Formula (D-3-4)

In the formula (D-3-4), R ^c1 , R ^c2 , n _c2 and n _c3 are the same as R ^a1 , R ^a2 , n _a2 and n _a3 in the formula (A4), respectively. In addition, in general formula (D-3-4), n _c1 is the number of repeating units, and represents the integer of 1-20. In addition, in general formula (E2-3-4), * represents a bond. For example, in the component (D-3), in the general formula (D-3-2), n _a2 is 3 or less, and the benzene ring to which the maleimide group is bonded is in the ortho position and the para position with respect to the maleimide group, When R ^a1 is not bonded to two or more, the structure represented by the above formula (D-3-4) may be included in combination with the structure represented by the formula (D-3-2). Further, for example, in the component (D-3), in the general formula (D-3-3), n _b2 is 3 or less, and the benzene ring to which the maleimide group binds is ortho-positioned and para-positioned to the maleimide group. Among them, when R ^b1 is not bonded to at least two of them, the structure represented by the above formula (D-3-4) may be included in combination with the structure represented by the formula (D-3-3). have.

(D-3) A component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

(D-3) Maleimide group equivalent of component becomes like this. Preferably it is 50 g/eq. or more, more preferably 100 g/eq. or more, particularly preferably 200 g/eq. or more, preferably 2000 g/eq. Hereinafter, more preferably 1000 g/eq. or less, particularly preferably 800 g/eq. is below. The maleimide group equivalent represents the mass of the maleimide compound per equivalent of the maleimide group. (E2-3) When the maleimide group equivalent of the component is within the above range, the effects of the present invention can be significantly obtained.

(D-3) There is no restriction|limiting in particular in the manufacturing method of a component. (D-3) component, for example, can be manufactured by the method described in Invention Association Publication No. 2020-500211. According to the manufacturing method described in this Invention Association Publication No. 2020-500211, a maleimide compound having a distribution in the number of repeating units of the trimethylindane skeleton can be obtained. The maleimide compound obtained by this method contains the structure represented by the following general formula (D-3-5). Therefore, (D-3) component may contain the maleimide compound containing the structure represented by general formula (D-3-5).

Formula (D-3-5)

(In the formula, R ¹ is, each independently, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, 6 to 10 carbon atoms an aryl group, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; R ² is each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon represents an aryloxy group having 6 to 10 atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group; n ₁ is 0.95 to 10.0 represents the average number of repeating units of; n ₂ each independently represents an integer of 0 to 4; n ₃ represents each independently an integer of 0 to 3. R ¹ represents an alkyl group, an alkyloxy group, an alkyl The hydrogen atom of thio group, aryl group, aryloxy group, arylthio group, and cycloalkyl group may be substituted with halogen atom Alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, aryl of R< ² > The hydrogen atom of the thio group and the cycloalkyl group may be substituted with a halogen atom. When n ₂ is 2 to 4, R ¹ may be the same or different in the same ring. When n ₃ is 2 to 3, R ² may be the same or different within the same ring.)

In the formula (D-3-5), R ¹ , R ² , n ₂ and n ₃ are the same as R ^a1 , R ^a2 , n _a2 and n _a3 in the formula (D-3-2), respectively. .

In the formula (D-3-5), n ₁ represents the average number of repeating units, and the range is 0.95 to 10.0. According to the manufacturing method described in Publication No. 2020-500211 of the Invention Association Publication No. 2020-500211, group 1 maleimide compounds including the structure represented by Chemical Formula (D-3-5) can be obtained. Maleimide comprising the structure represented by the formula (D-3-5) obtained in this way, as seen from the fact that the average number of repeating units n ₁ in the formula (D-3-5) can be smaller than 1.00 The compound may include a maleimide compound in which the number of repeating units of the trimethylindane skeleton is 0. Then, from the maleimide compound containing the structure represented by the formula (D-3-5), the maleimide compound having 0 repeating units in the trimethylindane skeleton is removed by purification to obtain the component (D-3), The resin composition may contain only the obtained (D-3) component. However, even when the maleimide compound of which the number of repeating units of the trimethylindane skeleton is 0 is contained in the resin composition, the effect of this invention can be acquired. Moreover, when a refinement|purification is abbreviate|omitted, suppression of cost is possible. Then, it is preferable that the resin composition contains the maleimide compound containing the structure represented by general formula (D-3-5) without removing the maleimide compound whose number of repeating units of a trimethylindane skeleton is 0.

In the general formula (D-3-5), the average number of repeating units n ₁ is preferably 0.95 or more, more preferably 0.98 or more, still more preferably 1.0 or more, particularly preferably 1.1 or more, and preferably It is 10.0 or less, More preferably, it is 8.0 or less, More preferably, it is 7.0 or less, Especially preferably, it is 6.0 or less. When the average number of repeating units n ₁ is within the above range, the effects of the present invention can be significantly obtained. In particular, the glass transition temperature of a resin composition can be raised effectively.

Examples of the structure represented by the general formula (D-3-5) include the following.

The maleimide compound including the structure represented by the formula (D-3-5) may further include a structure represented by the formula (D-3-4). For example, in the maleimide compound having a structure represented by the general formula (D-3-5), in the general formula (D-3-5), n ₂ is 3 or less and benzene to which the maleimide group is bonded. When R ¹ is not bonded to at least two of the ortho-position and para-position to the maleimide group of the ring, in combination with the structure represented by the formula (D-3-5), the formula (E2-3-4) It may include a structure represented by .

It is preferable that molecular weight distribution Mw/Mn computed from gel permeation chromatography (GPC) measurement exists in the specific range of the maleimide compound containing the structure represented by general formula (D-3-5). Molecular weight distribution is a value calculated|required by dividing the weight average molecular weight Mw by the number average molecular weight Mn, and it is represented by "Mw/Mn." Specifically, the molecular weight distribution Mw/Mn of the maleimide compound containing the structure represented by the general formula (D-3-5) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, still more preferably 1.2 to 3.6, particularly preferably 1.3 to 3.4. When the molecular weight distribution Mw/Mn of the maleimide compound having the structure represented by the formula (D-3-5) is within the above range, the effects of the present invention can be significantly obtained.

It is preferable that the quantity of the maleimide compound of which the average number of repeating units n< ₁ > is 0 among the maleimide compounds containing the structure represented by general formula (D-3-5) exists in a specific range. When the above GPC measurement of a maleimide compound having a structure represented by the formula (D-3-5) is performed, the amount of the maleimide compound having an average number of repeating units n ₁ of 0 is determined based on the results of the GPC measurement. It can be expressed as area %. Specifically, in the chromatogram obtained by the GPC measurement, the average number of repeating units n ₁ with respect to the total area of the peaks of the maleimide compound containing the structure represented by the formula (D-3-5) is 0 By the ratio (area %) of the area of the peak of the maleimide compound, the amount of the maleimide compound in which the average number of repeating units n ₁ is 0 can be expressed. Specifically, the amount of the maleimide compound having an average number of repeating units n ₁ of 0 with respect to 100 area % of the total amount of the maleimide compound having the structure represented by the formula (D-3-5) is preferably 32 areas. % or less, more preferably 30 area% or less, still more preferably 28 area% or less. When the amount of the maleimide compound having an average number of repeating units n ₁ of 0 is within the above range, the effects of the present invention can be significantly obtained.

It is preferable that the maleimide group equivalent of the maleimide compound containing the structure represented by Formula (D-3-5) exists in the same range as the maleimide group equivalent of the above-mentioned (D-3) component. When the maleimide group equivalent of the maleimide compound having the structure represented by the formula (D-3-5) is within the above range, the effects of the present invention can be significantly obtained.

(D) The content of the component is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product having low dielectric properties and excellent peel strength. 0.5 mass % or more, More preferably, it is 1 mass % or more, Preferably it is 10 mass % or less, More preferably, it is 8 mass % or less, More preferably, it is 5 mass % or less.

(D) As content of component, when the resin component in a resin composition is 100 mass % from a viewpoint of obtaining the hardened|cured material which is low in a dielectric characteristic and excellent in peeling strength, Preferably it is 1 mass % or more, More preferably, it is 3 mass %. % or more, more preferably 5 mass % or more, preferably 20 mass % or less, more preferably 15 mass % or less, still more preferably 10 mass % or less.

<(E) Inorganic filler>

The resin composition may contain the (E) inorganic filler as arbitrary components other than the component mentioned above. (E) By containing an inorganic filler in a resin composition, it becomes possible to obtain the hardened|cured material excellent in a dielectric characteristic.

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, carbonic acid Calcium, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, zircon Barium acid, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, etc. are mentioned. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as a silica, spherical silica is preferable. (E) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(E) As a commercial item of an inorganic filler, "UFP-30" by a Denka Chemical Co., Ltd. product, for example; "SP60-05", "SP507-05" by the Shin-Nitetsu Sumikin Materials company; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Corporation; "UFP-30" by Denka Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2050-SXF" manufactured by Adomatex Corporation; and the like.

(E) The average particle diameter of the inorganic filler is preferably 0.01 µm or more, more preferably 0.05 µm or more, particularly preferably 0.1 µm or more, from the viewpoint of significantly obtaining the desired effect of the present invention, preferably 5 It is micrometer or less, More preferably, it is 2 micrometers or less, More preferably, it is 1 micrometer or less.

(E) The average particle diameter of an inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring apparatus, and making the intermediate diameter into an average particle diameter. As the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial bottle, and what was dispersed for 10 minutes by ultrasonic wave can be used. For the measurement sample, using a laser diffraction particle size distribution measuring device, using a light source wavelength as blue and red, measuring the volume-based particle size distribution of the inorganic filler by a flow cell method, and measuring the median diameter from the obtained particle size distribution to calculate the average particle diameter. As a laser diffraction type particle size distribution measuring apparatus, "LA-960" by Horiba Corporation, "SALD-2200" by Shimadzu Corporation, etc. are mentioned, for example.

(E) The specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, particularly preferably 3 m 2 /g or more from the viewpoint of significantly obtaining the desired effect of the present invention. . Although there is no particular restriction on the upper limit, it is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area is measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec), by adsorbing nitrogen gas to the sample surface, and calculating the specific surface area using the BET multi-point method to measure the specific surface area of the inorganic filler can be obtained by

(E) It is preferable that the inorganic filler is treated with the surface treating agent from a viewpoint of improving moisture resistance and dispersibility. As a surface treatment agent, For example, Fluorine-containing silane coupling agents, such as 3,3,3-trifluoropropyl trimethoxysilane; aminosilane-based coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; Epoxysilane-type coupling agents, such as 3-glycidoxy propyl trimethoxysilane; mercaptosilane-based coupling agents such as 3-mercaptopropyltrimethoxysilane; silane-based coupling agent; alkoxysilanes such as phenyltrimethoxysilane; Organosilazane compounds, such as hexamethyldisilazane, a titanate type coupling agent, etc. are mentioned. In addition, a surface treatment agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

As a commercial item of a surface treatment agent, For example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. make "KBM803" (3-mercaptopropyltrimethoxy) silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical “SZ-31” (hexamethyldisilazane) manufactured by Koji Corporation, “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM-4803” manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane couple) ring agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyl trimethoxysilane), etc. are mentioned.

It is preferable that the grade of the surface treatment by a surface treating agent falls within a predetermined range from a viewpoint of the dispersibility improvement of an inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, preferably at 0.2 parts by mass to 3 parts by mass, and 0.3 parts by mass to 2 parts by mass. It is preferable that it is surface-treated.

The grade of the surface treatment by a surface treating agent can be evaluated by the amount of carbon per unit surface area of an inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler 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 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

(E) The amount of carbon per unit surface area of an inorganic filler can be measured, after washing-processing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, MEK in a sufficient amount as a solvent is added to the inorganic filler surface-treated with a surface treatment 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" by Horiba Corporation, etc. can be used.

(E) As the content of the inorganic filler, from the viewpoint of significantly obtaining the effect of the present invention, when the nonvolatile component in the resin composition is 100% by mass, preferably 40% by mass or more, more preferably 45% by mass or more, More preferably, it is 50 mass % or more, Preferably it is 75 mass % or less, Preferably it is 70 mass % or less, Preferably it is 65 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 55 mass % or less. mass% or less.

<(F) curing agent>

The resin composition may further contain the (F) hardening|curing agent as arbitrary components other than the component mentioned above. However, the (C) active ester curing agent is not included in the (F) curing agent. (F) Examples of the curing agent include a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. Among them, from the viewpoint of improving insulation reliability, (F) the curing agent is preferably at least one of a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent, a phenol-based curing agent and It is more preferable that it is any one of naphthol-type hardening|curing agents, and it is still more preferable that a phenol-type hardening|curing agent is included. (F) A hardening|curing agent may be used individually by 1 type, or may use 2 or more types together.

As the phenolic curing agent and the naphthol curing agent, from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolak structure or a naphthol curing agent having a novolak structure is preferable. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenolic hardening|curing agent is preferable, and a triazine skeleton containing phenolic hardening|curing agent is more preferable.

As a specific example of a phenol type hardening|curing agent and a naphthol type hardening|curing agent, For example, Meiwa Kasei Corporation "MEH-7700", "MEH-7810", "MEH-7851", Nippon Kayaku Corporation "NHN", "CBN" ”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd. ', "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA3018-50P", "EXB-9500" by DIC company etc. are mentioned.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by Showa Kobunshi, "P-d" by Shikoku Chemical Co., Ltd., and "F-a" are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cya Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, etc., these cyanate resins partially triazined A prepolymer etc. are mentioned. As a specific example of a cyanate ester type hardening|curing agent, "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin) manufactured by Ronza Japan, "ULL-950S" (polyfunctional cyanate ester resin), "BA230" ", "BA230S75" (a prepolymer in which a part or all of bisphenol A dicyanate was triazine-ized and became a trimer) etc. are mentioned.

As a specific example of a carbodiimide-type hardening|curing agent, "V-03", "V-07" by a Nisshinbo Chemical company, etc. are mentioned.

When a curing agent is included as a component (F), the ratio of the epoxy resin to (B) active ester curing agent and (F) curing agent is [the total number of epoxy groups in the epoxy resin]: [(B) active ester curing agent and ( F) total number of active groups of the curing agent], preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and still more preferably 1:0.5 to 1:2. Here, "the number of epoxy groups of an epoxy resin" is the value which summed up all the values obtained by dividing the mass of the nonvolatile component of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of the (B) active ester-based curing agent and (F) curing agent" is the sum of all the values obtained by dividing the mass of the active ester-based curing agent and the non-volatile component of the curing agent present in the resin composition by the active group equivalent. . As component (B) and component (F), the effect of this invention can be acquired remarkably by making the ratio with an epoxy resin into these ranges.

When a curing agent is included as a component (F), the amount ratio of the epoxy resin and all (F) curing agents is [the total number of epoxy groups in the epoxy resin]: [the total number of active groups in the (F) curing agent] in a ratio of 1: The range of 0.01 to 1:1 is preferable, 1:0.03 to 1:0.5 are more preferable, and 1:0.05 to 1:0.3 are still more preferable. Here, "the number of active groups of (F) hardening|curing agent" is the sum total of the value obtained by dividing the mass of the nonvolatile component of (F) hardening|curing agent which exists in a resin composition by the active-group equivalent. (F) As a component, by making the ratio of an epoxy resin and a hardening|curing agent into this range, the effect of this invention can be acquired remarkably.

(F) the content of the curing agent is preferably 1% by mass or more, more preferably 1.5% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of significantly obtaining the desired effect of the present invention; More preferably, it is 2 mass % or more. An upper limit becomes like this. Preferably it is 5 mass % or less, More preferably, it is 4 mass % or less, More preferably, it is 3 mass % or less.

(F) The content of the curing agent is preferably 1% by mass or more, more preferably 2% by mass or more, when the resin component in the resin composition is 100% by mass from the viewpoint of significantly obtaining the desired effect of the present invention. Preferably it is 3 mass % or more, Preferably it is 10 mass % or less, More preferably, it is 8 mass % or less, More preferably, it is 5 mass % or less.

<(G) curing accelerator>

The resin composition may contain the hardening accelerator as (G)component further as an arbitrary component other than the component mentioned above.

(G) As a component, a phosphorus type hardening accelerator, an amine type hardening accelerator, an imidazole type hardening accelerator, a guanidine type hardening accelerator, a metal type hardening accelerator, etc. are mentioned, for example. (G) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphoniumdecanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Silimidazolyl-(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-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, imidazole compounds and epoxy resins of adducts, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As an imidazole type hardening accelerator, you may use a commercial item, for example, "P200-H50" by a Mitsubishi Chemical company, etc. are mentioned.

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

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and tin, is mentioned, for example. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, zinc(II)acetylacetonate, and the like. organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(G) The content of the component, from the viewpoint of significantly obtaining the desired effect of the present invention, when the nonvolatile component in the resin composition is 100 mass%, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, More preferably, it is 0.1 mass % or more, Preferably it is 3 mass % or less, More preferably, it is 1.5 mass % or less, More preferably, it is 1 mass % or less.

(G) The content of the component is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, when the resin component in the resin composition is 100% by mass from the viewpoint of significantly obtaining the desired effect of the present invention. Preferably it is 0.5 mass % or more, Preferably it is 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 1 mass % or less.

<(H) Other additives>

The resin composition may further contain other additives as arbitrary components other than the component mentioned above. Examples of such additives include thermoplastic resins, elastomers, organic fillers, thickeners, defoamers, leveling agents, adhesion imparting agents, flame retardants, and the like. These may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

A resin composition can be manufactured by mixing the above-mentioned component in arbitrary order, for example. Further, in the process of mixing each component, heating and/or cooling may be performed by appropriately adjusting the temperature. In addition, during or after mixing of each component, stirring may be performed using a stirring apparatus, such as a mixer, to disperse|distribute each component uniformly. Moreover, you may perform a defoaming process to a resin composition as needed.

<Physical properties and uses of the resin composition>

Since the resin composition contains the component (A), component (B), and component (C) in combination, a cured product having low dielectric properties and excellent peel strength even with small surface roughness and high glass transition temperature can be obtained. .

A cured product obtained by thermosetting the resin composition at 200°C for 90 minutes has a low dielectric constant Dk. Accordingly, when an insulating layer is formed from this cured product, an insulating layer having a low dielectric constant can be obtained. For example, the dielectric constant Dk of the hardened|cured material obtained by hardening|curing a resin composition under the conditions described in the Example mentioned later becomes like this. Preferably it is 3.0 or less, More preferably, it is 2.9 or less, More preferably, it is 2.8 or less. The lower limit of the dielectric constant Dk of the cured product is not particularly limited, but may be 0.1 or more. The dielectric constant of hardened|cured material can be measured by the method demonstrated in an Example.

A cured product obtained by thermosetting the resin composition at 200°C for 90 minutes has a low dielectric loss tangent. Accordingly, when an insulating layer is formed from this cured product, an insulating layer having a low dielectric loss tangent can be obtained. For example, the dielectric loss tangent Df of the cured product obtained by curing the resin composition under the conditions described in Examples to be described later is preferably 0.010 or less, more preferably 0.005 or less, and still more preferably 0.004 or less. The lower limit of the dielectric constant Df of the cured product is not particularly limited, but may be 0.001 or more. The dielectric loss tangent of hardened|cured material can be measured by the method demonstrated in an Example.

The hardened|cured material obtained by thermosetting a resin composition at 200 degreeC for 90 minute(s) can make high the plating peeling strength which shows the adhesive strength between plating conductor layers. Therefore, when an insulating layer is formed with this hardened|cured material, the insulating layer with high peeling strength between a conductor layer can be obtained. For example, when the insulating layer and the plated conductor layer are formed by the method described in Examples to be described later, the peel strength between the insulating layer and the conductor layer is preferably 0.2 kgf/cm or more, more preferably may be 0.3 kgf/cm or more, particularly preferably 0.4 kgf/cm or more. Although the upper limit of adhesiveness is not specifically limited, For example, it may be 10.0 kgf/cm or less. Peel strength can be measured by the method demonstrated in an Example.

The hardened|cured material which thermosetted the resin composition at 200 degreeC for 90 minute(s) shows the characteristic that the arithmetic mean roughness (Ra) of the hardened|cured material surface after a roughening process can be made small. Therefore, the insulating layer with small arithmetic mean roughness Ra of the surface after a roughening process can be obtained. As arithmetic mean roughness Ra, Preferably it is 100 nm or less, More preferably, it is 80 nm or less, More preferably, it is 50 nm or less. The lower limit is not particularly limited, but may be 1 nm or more. Arithmetic mean roughness Ra can be measured according to the method described in the Example mentioned later.

The hardened|cured material obtained by thermosetting a resin composition at 200 degreeC for 90 minute(s) shows the characteristic that a glass transition temperature is high. Therefore, when the insulating layer is formed from this insulating layer, an insulating layer having a high glass transition temperature and excellent heat resistance can be obtained. As a glass transition temperature, Preferably it is 140 degreeC or more, More preferably, it is 145 degreeC or more, More preferably, it is 150 degreeC or more. Although the upper limit is not specifically limited, It can be set as 300 degrees C or less, etc. The glass transition temperature can be measured according to the method described in the Examples described later.

The resin composition which concerns on one Embodiment of this invention is suitable as a resin composition for insulation use, Especially, it is especially suitable as a resin composition for insulation layer formation. Therefore, for example, a resin composition is suitable as a resin composition for forming the insulating layer of a printed wiring board (resin composition for insulating layer formation of a printed wiring board). In addition, the resin composition is suitable as a resin composition (resin composition for forming an insulating layer for forming a conductor layer) for forming the insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer. do. The resin composition also includes a resin sheet, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, a component embedding resin, a multi-chip package, a package-on-package, a wafer level package, It can be widely used in applications where a resin composition can be used, such as a panel level package and a system-in-package.

In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment is used to form a redistribution forming layer as an insulating layer for forming a redistribution layer. It is suitable also as a resin composition (resin composition for rewiring forming layer formation) for this purpose, and a resin composition (resin composition for semiconductor chip sealing) for sealing a semiconductor chip. When the semiconductor chip package is manufactured, on the sealing layer, a redistribution layer may be further formed.

(1) the step of laminating a temporarily fixed film on the substrate,

(2) the step of temporarily fixing the semiconductor chip on the temporarily fixing film,

(3) forming a sealing layer on the semiconductor chip;

(4) the step of peeling the substrate and the temporarily fixed film from the semiconductor chip,

(5) a step of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporarily fixed film are peeled, and

(6) Step of forming a redistribution layer as a conductor layer on the redistribution forming layer

The resin composition mentioned above can be used also when a printed wiring board is a circuit board with a built-in component.

[Resin Sheet]

The resin sheet of this invention contains a support body and the resin composition layer provided on the said support body and formed from the resin composition of this invention.

The thickness of the resin composition layer is preferably 50 µm or less, more preferably 40 µm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film; More preferably, it is 30 micrometers or less. Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 5 micrometers or more, etc.

As a support body, the film which consists of a plastic material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastic material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). .) polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES) ), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

A support body may give a mat treatment, a corona treatment, and an antistatic treatment to the surface to join with the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface to join with the resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example. A commercial item may be used for the support body with a release layer, for example, "SK-1", "AL-5", "AL-" by Lintec which is a PET film which has a release layer which has an alkyd resin type mold release agent as a main component. 7", "Lumira T60" by Tore Corporation, "Purex" by Teijin Corporation, "Uni-pil" by Unichika Corporation, etc. are mentioned.

Although it does not specifically limit as thickness of a support body, The range of 5 micrometers - 75 micrometers is preferable, and the range of 10 micrometers - 60 micrometers is more preferable. On the other hand, when using a support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is the said range.

In one embodiment, the resin sheet may further contain the other layer as needed. As such another layer, the protective film according to the support body etc. which were provided in the surface which is not joined to the support body of a resin composition layer (namely, the surface on the opposite side to a support body), etc. are mentioned, for example. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be suppressed.

The resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish to a support using a die coater, etc., and further drying to form a resin composition layer. .

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; Amide solvents, such as dimethylformamide, dimethylacetamide (DMac), and N-methylpyrrolidone, etc. are mentioned. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as a heating and hot air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it also varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30 mass % to 60 mass % of an organic solvent, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, the resin composition layer can form.

A resin sheet can be wound up and stored in roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a protective film.

[Printed wiring board]

The printed wiring board which concerns on one Embodiment of this invention contains the insulating layer formed with the hardened|cured material obtained by hardening|curing the above-mentioned resin composition.

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet, for example.

(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate

(II) Step of curing the resin composition layer to form an insulating layer

The "inner-layer substrate" used in the step (I) is a member used as a substrate for a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene. An ether substrate etc. are mentioned. Moreover, the said board|substrate may have a conductor layer on the one side or both surfaces, and this conductor layer may be pattern-processed. An inner-layer substrate in which a conductor layer is formed on one or both surfaces of the substrate is sometimes referred to as an "inner-layer circuit board". Moreover, when manufacturing a printed wiring board, the intermediate product in which an insulating layer and/or a conductor layer should further be formed is also contained in "inner-layer board|substrate". When a printed wiring board is a circuit board with a built-in component, you may use the inner-layer board which incorporated the component.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-compressing the resin sheet to the inner layer substrate from the support side. As a member (hereinafter also referred to as a "thermal compression member") for heat-bonding the resin sheet to the inner layer substrate, a heated metal plate (such as a SUS head plate) or a metal roll (such as a SUS roll) is exemplified. On the other hand, it is preferable not to press the thermocompression-bonding member directly to the resin sheet, but to press through an elastic material, such as a heat-resistant rubber, so that the resin sheet may fully follow the surface unevenness|corrugation of an inner-layer board|substrate.

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

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressure laminator by the Meiki Sesakusho company, the vacuum applicator by the Nikko Materials company, a batch type vacuum pressure laminator, etc. are mentioned, for example.

After lamination, a smoothing treatment of the laminated resin sheet may be performed under atmospheric pressure, for example, by pressing the thermocompression-bonding member from the support side. The press conditions of the smoothing process can be made into the conditions similar to the thermocompression-bonding conditions of the said lamination|stacking. A smoothing process can be performed with a commercially available laminator. In addition, the lamination|stacking and smoothing process may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In the step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. Curing conditions of a resin composition layer are not specifically limited, You may use the conditions employ|adopted when forming the insulating layer of a printed wiring board. Although you may harden a resin composition layer by irradiation of active energy rays, such as an ultraviolet-ray, it is made to thermoset by heating normally.

For example, the thermosetting conditions of the resin composition layer also vary depending on the type of the resin composition, but in one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, More preferably, it is 170 degreeC - 210 degreeC. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.

Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature. For example, prior to thermosetting the resin composition layer, at a temperature of 50 ° C. to 120 ° C., preferably 60 ° C. to 115 ° C., more preferably 70 ° C. to 110 ° C., for 5 minutes or more, Preferably, you may preheat for 5 minutes - 150 minutes, More preferably, it is 15 minutes - 120 minutes, More preferably, it is 15 minutes - 100 minutes.

The method of manufacturing a printed wiring board may further include (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. When the support is removed after the step (II), the support is removed between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and (V). may be carried out in In addition, if necessary, the formation of the insulating layer and the conductor layer in the steps (I) to (V) may be repeated to form a multilayer wiring board.

Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Depending on the composition of the resin composition used for formation of an insulating layer, you may implement a process (III) using a drill, a laser, plasma, etc., for example. You may determine the dimension and shape of a hole suitably according to the design of a printed wiring board.

Process (IV) is a process of roughening an insulating layer. Usually, in this process (IV), the removal of smear is also performed. The procedure and conditions of a roughening process are not specifically limited. For example, the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid can be performed in this order, and an insulating layer can be roughened.

As a swelling liquid used for a roughening process, an alkali solution, surfactant solution, etc. are mentioned, for example, Preferably it is an alkali solution. As an alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Security P", "Swelling Deep Security SBU" by Atotech Japan, etc. are mentioned, for example. The swelling treatment by the swelling liquid is not particularly limited, and for example, it can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

As an oxidizing agent used for a roughening process, the alkaline permanganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned, for example. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Moreover, as for the density|concentration of the permanganate in an alkaline permanganic acid solution, 5 mass % - 10 mass % are preferable. As a commercially available oxidizing agent, alkaline-manganic acid solutions, such as "Concentrate Compact CP" and "Dosing Solution Securigans P" by Atotech Japan, are mentioned, for example.

As a neutralizing liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "reduction solution securigant P" by Atotech Japan company is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. The method of immersing the target object roughened by the oxidizing agent from points, such as workability|operativity, in the neutralization liquid of 40 degreeC - 70 degreeC for 5 minutes - 20 minutes is preferable.

In one embodiment, arithmetic mean roughness Ra of the insulating layer surface after a roughening process becomes like this. Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. The lower limit is not particularly limited, and may be, for example, 1 nm or more, 2 nm or more. Moreover, the root mean square roughness (Rq) of the surface of the insulating layer after roughening becomes like this. Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. It does not specifically limit about a lower limit, For example, it can be set as 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter.

A process (V) is a process of forming a conductor layer, and forms a conductor layer on an insulating layer. The conductor material used for a conductor layer is not specifically limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and as the alloy layer, for example, an alloy of two or more metals selected from the group described above (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium) a layer formed of an alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy , a copper/titanium alloy alloy layer is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel/chromium alloy is more preferable, and a single metal layer of copper This is more preferable.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the 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 a nickel-chromium alloy.

Although the thickness of a conductor layer depends on the design of a desired printed wiring board, it is 3 micrometers - 35 micrometers generally, Preferably it is 5 micrometers - 30 micrometers.

The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a method such as a semi-additive method or a full additive method. It is preferable to form by the semi-additive method from a viewpoint of the simplicity of manufacture. Hereinafter, an example in which the conductor layer is formed by a semi-additive method is shown.

A plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to the desired wiring pattern is formed. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[Semiconductor device]

A semiconductor device according to an embodiment of the present invention includes the printed wiring board described above. This semiconductor device can be manufactured using the printed wiring board mentioned above.

Examples of the semiconductor device include various semiconductor devices provided for electric products (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trams, ships, and aircraft). have.

[Example]

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operation described below was performed in an environment of normal temperature and normal pressure, unless otherwise specified.

<Preparation of maleimide resin A>

A MEK solution (70% by mass of nonvolatile components) of maleimide resin A synthesized by the method described in Synthesis Example 1 of Invention Association Publication No. 2020-500211 was prepared. This maleimide resin A has a structure represented by a following formula.

When the FD-MS spectrum of maleimide resin A is measured, the peaks of M+=560, 718, and 876 are confirmed. These peaks correspond to the case where n ₁ is 0, 1, and 2, respectively. Further, when the maleimide resin A is analyzed by GPC and the value of the number of repeating units n ₁ of the indane skeleton moiety is determined based on the number average molecular weight, n ₁ =1.47 and molecular weight distribution (Mw/Mn) = 1.81. In addition, in 100 area% of the total amount _of maleimide compound A1, the content rate of the maleimide resin of which the average number of repeating units n1 is ₀ is 26.5 area%.

The FD-MS spectrum of said maleimide resin A shows what was measured by the following measuring apparatus and measurement conditions.

(FD-MS spectrum measurement device and measurement conditions)

Measuring device: JMS-T100GC AccuTOF

Measuring conditions

Measuring range: m/z=4.00 to 2000.00

Rate of change: 51.2mA/min

Final current value: 45mA

Cathode voltage: -10kV

Logging Interval: 0.07sec

GPC of said maleimide resin A shows what was measured by the following measuring apparatus and measurement conditions.

Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation

Column: Guard column "HXL-L" by Tosoh Corporation, "TSK-GEL G2000HXL" by Tosoh Corporation, "TSK-GEL G2000HXL" by Tosoh Corporation, "TSK-GEL G3000HXL" by Tosoh Corporation, and "TSK-GEL G3000HXL" by Tosoh Corporation -GEL G4000HXL”

Detector: RI (Differential Refractometer)

Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40°C

Developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: Monodisperse polystyrene of known molecular weight is used in accordance with the measurement manual of "GPC Workstation EcoSEC-WorkStation".

Sample: What filtered the 1.0 mass % tetrahydrofuran solution in conversion of the nonvolatile component of a maleimide compound with a microfilter (50 microliters).

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of maleimide resin A, and the average number of repeating units contributing to the indane skeleton in the maleimide resin, "n ₁ ," were determined by the above GPC measurement. What was computed from the obtained GPC chart is shown. In addition, the average number _of repeating units "n1" shows what was computed based on the number average molecular weight (Mn). Specifically, with respect to the compound having n ₁ of 0 to 4, the theoretical molecular weight and the actual molecular weight in GPC are plotted on the scatter plot, and an approximate straight line is drawn. And the number average molecular weight (Mn) is calculated|required from the point shown by the measured value Mn( ₁ ) on this straight line, and also computed average number of repeating units "n1". In addition, based on the result of GPC measurement, the content rate (area %) of the maleimide resin of which the average number _of repeating units n1 is 0 in 100 area% of total amount of maleimide resin A is computed. For details, reference may be made to Invention Association Publication No. 2020-500211.

<Synthesis of PEEK (polyether ether ketone) compound A>

In a 500 mL flask (3 necks) equipped with a stirring device, an argon inlet tube, and a Dean Stark device, 31.443 g of 4,4'-difluorobenzophenone, 13.223 g of resorcinol, 29.894 g of anhydrous potassium carbonate, N-methyl 180 mL of pyrrolidone and 90 mL of toluene were added, heated while stirring in an argon atmosphere, and toluene was refluxed at 130 to 140°C for 4 hours. Then, it further heated and toluene was distilled off at 170-180 degreeC. Furthermore, after continuing stirring at 170-180 degreeC for 10 hours, it returned to room temperature, and obtained the product 1.

To the flask containing the product 1, 5.233 g of 4-aminophenol, 6.628 g of anhydrous potassium carbonate, 18 mL of N-methylpyrrolidone, and 90 mL of toluene were added, and heated while stirring under an argon atmosphere, and heated at 130 to 140°C for 3 Time toluene was refluxed. Then, it heated and distilled off toluene at 170-180 degreeC, and stirring was continued for 4 hours, maintaining the said temperature. Then, it cooled to room temperature, and powdery solid was obtained by adding and filtering the reaction liquid to 5000 mL of methanol. This powdery solid was repeatedly washed with methanol and water, and then dried at 100°C for 8 hours to obtain 37.461 g of a powdery solid (Diamine-A).

0.878 g of Diamine-A, 4.943 g of maleic anhydride, and 240 mL of N-methylpyrrolidone were placed in a 500 mL flask (3 neck) equipped with a stirrer and an argon inlet tube, and the mixture was stirred at room temperature under an argon atmosphere for 18 hours. . Then, 8.576 g of acetic anhydride and 0.689 g of sodium acetate were added, and it stirred at 60 degreeC for 6 hours. After returning the reaction liquid to room temperature, powdery solid was obtained by adding the reaction liquid to 5000 mL of methanol. After washing this powdery solid repeatedly with methanol and water, it dried at 100 degreeC for 8 hours, and 28.434g of PEEK compounds A represented by the following formula were obtained. The number average molecular weight calculated by GPC measurement of PEEK compound A was 2230.

[Example 1]

14 parts of PEEK compound A, naphthalene type epoxy resin (“ESN475V” manufactured by Nippon-Sumikin Chemical Co., Ltd., epoxy equivalent about 332 g/eq.) 20 parts, active ester curing agent (“HPC-8000-65T” manufactured by DIC), active group Equivalent 223, toluene solution having a solid content of 65 mass%) 30 parts, an inorganic filler (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd. “KBM573”)) surface-treated spherical silica (“SO-C2” manufactured by Adomatex Co., Ltd.) , average particle diameter 0.5 μm, specific surface area 5.8 m 2 /g) 60 parts, and 0.5 parts of a curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 2-phenyl-1-benzyl-1H-imidazole) are mixed, and a high-speed rotary mixer It was uniformly dispersed using a resin varnish.

As a support body, the polyethylene terephthalate film ("AL5" by Lintec company, 38 micrometers in thickness) provided with the mold release layer was prepared. On the release layer of this support body, said resin varnish was apply|coated uniformly so that the thickness of the resin composition layer after drying might be set to 40 micrometers. Then, the resin varnish was dried at 80 degreeC - 100 degreeC (average 90 degreeC) for 4 minutes, and the resin sheet containing a support body and a resin composition layer was obtained.

[Example 2]

In Example 1, 30 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC, 223 active group equivalent, and a toluene solution having a solid content of 65% by mass) was added to 30 parts of an active ester-based curing agent (“HPC-8150-” manufactured by DIC). 62T", active group equivalent of 229, toluene solution having a solid content of 62% by mass)) was replaced with 30 parts.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Example 3]

In Example 2,

change the amount of PEEK compound A from 14 parts to 10.5 parts,

Further radically polymerizable compound (biphenyl aralkyl maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., MEK/toluene mixed solution containing 70% of nonvolatile matter)) 5 wealth was used.

Except for the above, it carried out similarly to Example 2, and obtained the resin varnish and the resin sheet.

[Example 4]

In Example 2,

change the amount of PEEK compound A from 14 parts to 12.6 parts,

Furthermore, 2 parts of radically polymerizable compounds ("BMI-1500" by Designer Molecules, maleimide group equivalent 750 g/eq.) were used.

Except for the above, it carried out similarly to Example 2, and obtained the resin varnish and the resin sheet.

[Example 5]

In Example 2,

Change the amount of the active ester curing agent (“HPC-8150-62T” manufactured by DIC, 229 active group equivalent, toluene solution having a solid content of 62% by mass) from 30 parts to 25 parts,

Change the amount of the curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 2-phenyl-1-benzyl-1H-imidazole) from 0.5 part to 0.1 part,

Further, 5 parts of a triazine skeleton-containing cresol novolac curing agent ("LA3018-50P" manufactured by DIC, 151 hydroxyl equivalent, and a 50% nonvolatile component 1-methoxy-2-propanol solution) was used.

Except for the above, it carried out similarly to Example 2, and obtained the resin varnish and the resin sheet.

[Example 6]

In Example 2,

change the amount of PEEK compound A from 14 parts to 10.5 parts,

In addition, 5 parts of maleimide resin A were used.

Except for the above, it carried out similarly to Example 2, and obtained the resin varnish and the resin sheet.

[Example 7]

In Example 1, 30 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC, 223 active group equivalent, and a toluene solution having a solid content of 65% by mass) was added to 30 parts of an active ester-based curing agent containing a naphthalene structure (Airwater Corporation). Manufactured "PC1300-02-65MA", active group equivalent 200, methyl amyl ketone solution of solid content 65 mass %) was replaced with 30 parts.

Except for the above, it carried out similarly to Example 1, and obtained the resin varnish and the resin sheet.

[Comparative Example 1]

In Example 2,

without using 14 parts of PEEK compound A,

Spherical silica surface-treated with an inorganic filler (amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm, specific surface area 5.8 m 2 /g) The amount of was changed from 60 parts to 45 parts.

Except for the above, it carried out similarly to Example 2, and obtained the resin varnish and the resin sheet.

[Comparative Example 2]

In Example 3,

Without using 10.5 parts of PEEK compound A,

The amount of the radically polymerizable compound (biphenylaralkyl maleimide compound ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g/eq., MEK/toluene mixed solution with 70% nonvolatile content)) Changed from 5 to 20.

Except for the above, it carried out similarly to Example 3, and obtained the resin varnish and the resin sheet.

[Comparative Example 3]

In Example 4,

Without using 12.6 parts of PEEK compound A,

The quantity of the radically polymerizable compound ("BMI-1500" by Designer Molecules, 750 g/eq. of maleimide group equivalent) was changed into 14 parts from 2 parts.

Except for the above, it carried out similarly to Example 4, and obtained the resin varnish and the resin sheet.

[Measurement of dielectric properties (permittivity and dielectric loss tangent)]

The resin sheet produced by the Example and the comparative example was heated at 200 degreeC for 90 minute(s), and the resin composition layer was thermosetted. Then, the support body was peeled, and "hardened|cured material A of a resin composition" was obtained. The cured product A of this resin composition was cut into a test piece having a width of 2 mm and a length of 80 mm. About the said test piece, the dielectric constant Dk and dielectric loss tangent Df were measured at the measurement frequency of 5.8 GHz, and the measurement temperature of 23 degreeC by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. Measurement was performed on three test pieces, and the average value is shown in the table below.

[Measurement of plating peel strength]

(1) Underlying treatment of inner-layer circuit board:

As an inner-layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate having an inner-layer circuit (copper foil) on both sides (copper foil thickness 18 µm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) was prepared. 1 micrometer of both surfaces of this inner-layer circuit board were etched with "CZ8101" by Mack, and the roughening process of the copper surface was performed.

(2) Lamination of resin sheet:

The resin sheet was laminated on both surfaces of the inner-layer circuit board using a batch-type vacuum pressure laminator (manufactured by Nikko Materials, a two-stage build-up laminator, CVP700). This lamination was performed so that the resin composition layer of a resin sheet might contact an inner-layer circuit board. In addition, this lamination was pressure-reduced for 30 second, the atmospheric pressure was 13 hPa or less, and it performed by crimping|bonding for 45 second at 130 degreeC and the pressure of 0.74 MPa. Then, hot pressing was performed at 120 DEG C and a pressure of 0.5 MPa for 75 seconds.

(3) curing of the resin composition:

The laminated resin sheet and inner-layer circuit board were heated at 130°C for 30 minutes and then heated at 170°C for 30 minutes to cure the resin composition to form an insulating layer. Then, the support body was peeled, and the laminated board provided with an insulating layer, an inner-layer circuit board, and an insulating layer in this order was obtained.

(4) Harmonization treatment:

The above laminated substrate was immersed in a swelling solution (Atotech Japan Co., Ltd. diethylene glycol monobutyl ether containing swelling deep securigant P (glycol ether, aqueous sodium hydroxide solution)) at 60° C. for 10 minutes. . Next, the laminated substrate was immersed in a roughening solution (Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) manufactured by Atotech Japan Co., Ltd. at 80° C. for 20 minutes. After that, The laminated substrate was immersed in a neutralizing solution (Reduction Soleucine Securigant P (aqueous solution of sulfuric acid) manufactured by Atotech Japan) for 5 minutes at 40° C. Then, the laminated substrate was dried at 80° C. for 30 minutes, , "evaluation substrate A" was obtained.

(5) Plating by semi-additive method:

The evaluation substrate A was immersed in a solution for electroless plating containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Then, it heated at 150 degreeC for 30 minutes, and performed annealing treatment. After that, an etching resist was formed, and pattern formation by etching was performed. Thereafter, copper sulfate electroplating was performed to form a conductor layer to a thickness of 20 µm. Then, the annealing treatment was performed at 200 degreeC for 60 minutes, and "evaluation board|substrate B" was obtained.

(6) Measurement of plating peel strength:

In the conductor layer of the evaluation substrate B, an incision surrounding a rectangular portion having a width of 10 mm and a length of 100 mm was formed. One end of the rectangular part was peeled off and picked up with a household tool (manufactured by TSE Co., Ltd., Autocom-type testing machine "AC-50C-SL"). The above rectangular portion was peeled off in the vertical direction at a speed of 50 mm/min in room temperature with a household tool, and the load (kgf/cm) when 35 mm was peeled off was measured as the plating peel strength.

[Measurement of surface roughness Ra]

The arithmetic mean roughness Ra of the surface of the insulating layer of the evaluation board|substrate A was measured. The measurement was performed using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Vico Instruments) in VSI mode and a 50x lens, with a measurement range of 121 µm x 92 µm. This measurement was performed at 10 measurement points, and the average value is shown in the following table|surface.

[Measurement of glass transition temperature]

The cured product A of the resin composition was cut into test pieces having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile weighting method using a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SII Nanotechnology). After attaching the test piece to the said apparatus, it measured under the measurement conditions of 200 mN load and 2 degreeC/min of temperature increase rate. The obtained peak top of tan-delta was computed as a glass transition temperature (degreeC).

* In a table|surface, content of (A) component shows content of (A) component at the time of making the resin component in a resin composition 100 mass %. (E) Content of component shows content of (E) component at the time of setting it as 100 mass % of non-volatile components in a resin composition. (C)component/(B)component shows the quantity ratio of (C)component and (B)component.

Claims (15)

(A) a polyether ether ketone compound having a maleimide group;
(B) an epoxy resin, and
(C) A resin composition comprising an active ester-based curing agent. The resin composition of Claim 1 whose number average molecular weight of (A) component is 10000 or less. The resin composition of Claim 1 in which (A) component has a maleimide group at the terminal. The resin composition of Claim 1 whose content of (A) component is 5 mass % or more and 60 mass % or less, when the resin component in a resin composition is 100 mass %. The resin composition according to claim 1, wherein the component (B) contains a naphthol-type epoxy resin. The resin composition according to claim 1, wherein the component (C) is at least one selected from a dicyclopentadiene type active ester curing agent and a naphthalene type active ester curing agent. The resin composition according to claim 1, further comprising (D) a resin having a polymerizable unsaturated group. The resin composition according to claim 7, wherein the component (D) is a resin containing a maleimide group and an aromatic ring. The resin composition according to claim 1, further comprising (E) an inorganic filler. The resin composition of Claim 9 whose content of (E) component is 40 mass % or more and 65 mass % or less, when the non-volatile component in a resin composition is 100 mass %. The resin composition according to claim 1, which is for forming an insulating layer. The resin composition according to claim 1, which is for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 12 provided on the support. The printed wiring board containing the insulating layer formed with the hardened|cured material of the resin composition in any one of Claims 1-12. A semiconductor device comprising the printed wiring board according to claim 14 .