KR20160002381A - Resin composition - Google Patents

Abstract

Provided is a resin composition capable of forming an insulating layer which is excellent in terms of dielectric tangent, thermal expansion, breaking point elongation, surface roughness, and peel strength, in the production of a printed wiring board. To this end, the resin composition comprises: (A) an epoxy resin; (B) an activated ester compound; (C) a carbodiimide compound; (D) a thermoplastic resin; and (E) an inorganic filler, wherein the content of the component (E) is 40 wt% with respect to 100 wt% of a non-volatile component in the resin composition.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. The present invention also relates to an adhesive film, a printed wiring board, and a semiconductor device using the resin composition.

As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately overlapped is known. In the build-up method, generally, the insulating layer is formed by curing the resin composition. For example, Patent Document 1 discloses a technique of curing a resin composition containing an epoxy resin, an active ester compound and a carbodiimide compound to form an insulating layer of low dielectric tangent (low dielectric tangent).

Although the number of stacked layers due to the buildup of the printed wiring board tends to increase due to the trend of thin slenderness in recent years, cracks and circuit deformation due to the difference in thermal expansion between the insulating layer and the conductor layer It becomes a problem. As a technique for suppressing the problem of such cracks and circuit deformation, for example, Patent Document 2 discloses a technique for suppressing the thermal expansion rate of the insulating layer formed to be low by increasing the content of the inorganic filler in the resin composition.

Patent Document 1: JP-A 2006-335834 Patent Document 2: JP-A-2010-202865

The inventors of the present invention conducted a test for blending a high content of an inorganic filler in the resin composition described in Patent Document 1 in order to form an insulating layer with low dielectric loss tangent and low thermal expansion coefficient at the time of manufacturing a printed wiring board. The resulting resin composition results in an insulating layer exhibiting a desired dielectric tangent and thermal expansion ratio, while when it comes to an insulating layer in which characteristics such as elongation at break, surface roughness, and peel strength are deteriorated The inventors of the present invention have found out that the present invention is not limited thereto.

An object of the present invention is to provide a resin composition capable of producing an insulating layer which is excellent in dielectric tangent, thermal expansion rate, elongation at break, surface roughness and peak strength at the time of manufacturing a printed wiring board.

The inventors of the present invention have made extensive studies on the above problems, and as a result, have found that the above-mentioned specific resin compositions can solve the above problems, and have completed the present invention.

That is, the present invention includes the following contents.

[1] A resin composition comprising (1) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) an inorganic filler, Wherein the amount of the non-volatile component is 40 mass% or more based on 100 mass% of the non-volatile component.

[2] The resin composition according to [1], wherein the component (D) has a weight average molecular weight of 10000 to 200000.

[3] The thermoplastic resin composition according to [1] or [2], wherein the component (D) is a thermoplastic resin having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom or a functional group containing a carbon- ≪ / RTI >

[4] The positive resist composition as described in [1], wherein the component (D) is at least one compound selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, a thiol group, The resin composition according to any one of [1] to [3], which is a thermoplastic resin having at least one functional group selected from the group consisting of an alkenyl group, an allene group and a ketene group.

[5] The resin composition according to [1], wherein the component (D) is at least one thermoplastic resin selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, a vinyl resin containing an acid anhydride group, a polyimide resin, a polyamideimide resin and a styrene- The resin composition according to any one of [1] to [4],

[6] The resin composition according to any one of [1] to [5], wherein the component (C) has a weight average molecular weight of 500 to 5,000.

[7] The resin composition according to any one of [1] to [6], wherein the NCO content of the component (C) is 5 mass% or less.

[8] The resin composition according to any one of [1] to [7], wherein the content of the component (E) is 50% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

[9] The resin composition according to any one of [1] to [8], wherein the component (E) has an average particle diameter of 0.01 μm to 3 μm.

[10] The resin composition according to any one of [1] to [9], wherein the component (E) is silica.

[11] The resin composition according to any one of [1] to [10], further comprising (F) a curing accelerator.

[12] The resin composition according to [11], wherein the component (F) is 4-dimethylaminopyridine or 1-benzyl-2-phenylimidazole.

[13] The resin composition according to any one of [1] to [12], wherein the resin composition is cured to form an insulating layer and the arithmetic mean roughness (Ra) after the surface of the insulating layer is roughened to 140 nm or less. Resin composition.

[14] The resin composition according to any one of [1] to [13], wherein the elongation at break of the cured product of the resin composition is 2% or more.

[15] The resin composition according to any one of [1] to [14], wherein the cured product of the resin composition has a glass transition temperature (Tg) of 165 ° C or more.

[16] An adhesive film comprising a support and a layer of the resin composition according to any one of [1] to [15] bonded to the support.

[17] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of [1] to [15].

[18] A semiconductor device comprising a printed wiring board according to [17].

According to the present invention, it is possible to provide a resin composition capable of producing an insulating layer excellent in dielectric tangent, thermal expansion rate, elongation at break, surface roughness and peak strength at the time of manufacturing a printed wiring board.

Hereinafter, the present invention will be described in detail based on its preferred embodiment.

[Resin composition]

The resin composition of the present invention comprises (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) an inorganic filler, Wherein the nonvolatile component in the resin composition is 40 mass% or more based on 100 mass% of the nonvolatile component.

(E) an inorganic filler in a high content in a resin composition containing (A) an epoxy resin, (B) an active ester compound and (C) a carbodiimide compound, the resulting resin composition has low dielectric loss tangent The present inventors have found that there is a case where an insulating layer exhibiting an expansion ratio is caused while a characteristic such as breaking point elongation, surface roughness, and peel strength is deteriorated. The resin composition of the present invention further contains (D) a thermoplastic resin, thereby making it possible to produce an insulating layer that is excellent in elongation at break, surface roughness and peel strength as it is with low dielectric loss tangent and low thermal expansion coefficient. In this respect, even when (D) a thermoplastic resin is added to the resin composition containing no active ester compound (B), the elongation at break, surface roughness and peel strength are not achieved. Also, even when the thermoplastic resin (D) is added to the resin composition containing no (C) carbodiimide compound, the desired breaking strength elongation, surface roughness and peel strength are not achieved. (E) When the thermoplastic resin (D) is added to the resin composition having a low content of the inorganic filler, the desired dielectric loss tangent and the thermal expansion coefficient can not be achieved. These are clearly grasped from the results of comparative examples which will be described later. In this way, the effect of the resin composition of the present invention can be obtained by adding (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin, Is a synergistic and synergistic effect.

Each component contained in the resin composition of the present invention will be described below.

≪ (A) Epoxy resin >

The resin composition of the present invention comprises an epoxy resin as the component (A).

Examples of the epoxy resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin having an ester skeleton, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, Spiro-ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin , Trimethylol-type epoxy resin, and tetraphenylethane-type epoxy resin. The epoxy resin may be used singly or in combination of two or more kinds.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100 mass%, it is preferable that at least 50 mass% or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and having a liquid epoxy resin (hereinafter referred to as " liquid epoxy resin ") at a temperature of 20 캜 and three or more epoxy groups in one molecule, (Hereinafter referred to as " solid epoxy resin "). When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Further, the fracture strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy Resin and an epoxy resin having a butadiene structure are preferable and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, alicyclic epoxy resin having ester skeleton, and naphthalene type epoxy resin are more preferable, A bisphenol A type epoxy resin and a bisphenol AF type epoxy resin are more preferable and a bisphenol AF type epoxy resin is particularly preferable from the viewpoint of excellent physical property balance of a cured product. Specific examples of the liquid epoxy resin include "HP4032", "HP4032H", "HP4032D", "HP4032SS" (naphthalene type epoxy resin), "828US" and "jER828EL" manufactured by Mitsubishi Kagaku (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "YL7760" (bisphenol AF type epoxy resin) EX-721 " (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., and ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) (Alicyclic epoxy resin having an ester skeleton) and " PB-3600 " (epoxy resin having a butadiene structure) of a cell preparation. These may be used singly or in combination of two or more kinds.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins , An anthracene type epoxy resin, a bisphenol A type epoxy resin and a tetraphenylethane type epoxy resin are preferable, and a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin and a biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolak type epoxy resin) EXA7311-G3 "," EXA7311-G4 "," EXA7311-G4S "," HP6000 "(dicyclopentadiene type epoxy resin) (Naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000" manufactured by Nippon Kayaku Co., , "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (biquilene type epoxy resin (biphenyl type epoxy resin)) manufactured by Kagaku Co., "YL8800" (anthracene epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Kagaku Co., "JER1010" (solid bisphenol A type epoxy resin) and "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Kagaku Co., Ltd., and the like.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is preferably in the range of 1: 0.1 to 1: 8 by mass ratio. By setting the proportions of the liquid epoxy resin and the solid epoxy resin in this range, it is possible to obtain sufficient flexibility when i) the adhesive is used in the form of an adhesive film, and ii) when it is used in the form of an adhesive film , Handling property is improved, and (iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 0.3 to 1: 7, : 0.6 to 1: 6.

The content of the epoxy resin in the resin composition is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, still more preferably 5% by mass to 35% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability By mass or more and 10% by mass to 35% by mass or 10% by mass to 30% by mass.

In the present invention, the content of each component in the resin composition is a value obtained by assuming that the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. With this range, the cross-linking density of the cured product becomes sufficient, resulting in an insulating layer having a small surface roughness. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of the resin containing one equivalent of epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

≪ (B) Active ester compound >

The resin composition of the present invention contains an active ester compound as the component (B).

The active ester compound is a compound having at least one active ester group in one molecule and can be used in combination with a carbodiimide compound (C), a thermoplastic resin (D) and an inorganic filler (E) , Thermal expansion rate, breaking point elongation, surface roughness, and peel strength.

The active ester compound is preferably a compound having two or more active ester groups in one molecule, and examples thereof include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds A compound having two or more ester groups having a high reaction activity in one molecule is preferably used. The active ester compound may be used singly or in combination of two or more kinds.

From the viewpoint of improving heat resistance, an active ester compound obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with at least one selected from a phenol compound, a naphthol compound and a thiol compound is more preferable, and an active ester compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group, An aromatic compound having at least two active ester groups in one molecule is more preferable and as the aromatic compound obtained by reacting a carboxylic acid compound having at least two carboxyl groups in one molecule with an aromatic compound having a phenolic hydroxyl group, More preferred are aromatic compounds having at least two active ester groups. The active ester compound may be in a linear form or in a branched form. In addition, if the carboxylic acid compound having at least two or more carboxyl groups in one molecule contains a fat chain, compatibility with the resin composition can be enhanced, and heat resistance can be enhanced if the compound has an aromatic ring.

Examples of the carboxylic acid compound include aliphatic carboxylic acids having 1 to 20 (preferably 2 to 10, more preferably 2 to 8) carbon atoms, aromatic groups having 7 to 20 carbon atoms (preferably 7 to 10) Carboxylic acid. Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid, and the like. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable.

The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid and thiobenzoic acid.

Examples of the phenol compound include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and still more preferably 6 to 22) phenol compounds, Methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzene, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol, and the like. As the phenol compound, a phenol novolak, a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 may be used.

Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20) carbon atoms, and specific examples include? -Naphthol,? -Naphthol, Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. As the naphthol compound, naphthol novolak may also be used.

Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol,? -Naphthol,? -Naphthol, 1,5-dihydroxynaphthalene, Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol, phenol novolak, The phosphorus atom-containing oligomer having a phenolic hydroxyl group is preferable, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri A phosphorus atom-containing oligomer having a phenolic hydroxyl group, and more preferably a 1,5-dihydroxybenzophenone, a tetrahydroxybenzophenone, a fluoroglucine, a benzenetriol, a dicyclopentadiene type diphenol, Dihydroxyl Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolak, The phosphorus atom-containing oligomer having a phenolic hydroxyl group is more preferred, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phenol Novolak, and phosphorus atom-containing oligomers having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type di Phenol, phosphorus atom containing oligomers having a phenolic hydroxyl group are even more preferred, and dicyclopentadiene type diphenols are particularly preferred.

The thiol compound is not particularly limited, and examples thereof include benzene dithiol, triazinedithiol and the like.

Suitable specific examples of the active ester compound include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolak, benzoyl phenol novolak An active ester compound containing an aromatic carboxylic acid and a phosphorus atom-containing oligomer having a phenolic hydroxyl group, and among these, an active ester compound containing a dicyclopentadiene type diphenol structure, a naphthalene Structure, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable. In the present invention, the "dicyclopentadiene type diphenol structure" refers to a divalent structural unit comprising phenylene-dicyclopentylene-phenylene.

More specifically, examples of the active ester compound having a dicyclopentadiene type diphenol structure include a compound represented by the following formula (1).

(Wherein R is a phenyl group or a naphthyl group, k is 0 or 1, and n is an average number of repeating units of 0.05 to 2.5)

R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5 from the viewpoint of lowering dielectric tangent and improving heat resistance.

As the active ester compound, an active ester compound disclosed in Japanese Patent Application Laid-Open Nos. 2004-277460 and 2013-40270 may be used, or a commercially available active ester compound may be used. EXB 9461, EXB 9460, EXB 9460S, HPC-8000-65T (manufactured by DIC Corporation), a naphthalene structure having a dicyclopentadiene-type diphenol structure as the active ester compound, EXB9416-70BK (manufactured by DIC Corporation) as an active ester compound, DC808 (manufactured by Mitsubishi Chemical Corp.) as an active ester compound containing an acetylated phenol novolac, benzoylated phenol novolak YLH1026 (manufactured by Mitsubishi Chemical Corp.) as the active ester compound, and EXB9050L-62M (DIC) as the phosphorus atom-containing active ester compound.

Excellent insulating properties in any of dielectric tangent, thermal expansion rate, breaking point elongation, surface roughness and peel strength in a combination of a carbodiimide compound (C), a thermoplastic resin (D), and an inorganic filler (E) The content of the active ester compound in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of obtaining a layer, in particular, from the viewpoint of obtaining an insulating layer exhibiting a low surface roughness and exhibiting a high peak strength, , And more preferably 5 mass% or more. The upper limit of the content of the active ester compound is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

When the number of epoxy groups in the epoxy resin (A) is 1, from the viewpoint of obtaining an insulating layer having a good mechanical strength, (B) the number of reactors of the active ester compound is preferably 0.2 to 2, more preferably 0.3 to 1.5 More preferably from 0.35 to 1. Here, the "number of epoxy groups of the epoxy resin" is a value obtained by dividing the value obtained by dividing the solid content of each epoxy resin present in the resin composition by the epoxy equivalent, for all epoxy resins. The term " reactor " means a functional group capable of reacting with an epoxy group. The term " reactor number of active ester compound " means the sum of values obtained by dividing the solid content of the active ester compound present in the resin composition by the reactor equivalent to be.

≪ (C) carbodiimide compound >

The resin composition of the present invention includes a carbodiimide compound as the component (C).

The carbodiimide compound is a compound having at least one carbodiimide group (-N═C═N-) in one molecule, and the active ester compound (B), the thermoplastic resin (D) to be described later, (E) inorganic filler, an insulating layer having excellent dielectric tangent, thermal expansion rate, elongation at break, surface roughness and peel strength can be obtained. As the carbodiimide compound, a compound having two or more carbodiimide groups in one molecule is preferable. The carbodiimide compound may be used alone, or two or more carbodiimide compounds may be used in combination.

In one embodiment, the carbodiimide compound contained in the resin composition of the present invention contains a structural unit represented by the following formula (2).

(Wherein X is an alkylene group, a cycloalkylene group or an arylene group, which may have a substituent, and p is an integer of 1 to 5. When a plurality of Xs exist, they may be the same or different. Is a binding number (binding hand)

The number of carbon atoms of the alkylene group represented by X is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms of the substituent group is not included in the number of carbon atoms in question. Suitable examples of the alkylene group include a methylene group, an ethylene group, a propylene group and a butylene group.

The number of carbon atoms of the cycloalkylene group represented by X is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. The number of carbon atoms of the substituent group is not included in the number of carbon atoms in question. Suitable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group and a cyclohexylene group.

The arylene group represented by X is a group obtained by removing two hydrogen atoms from aromatic hydrocarbons on the aromatic ring. The number of carbon atoms of the arylene group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The number of carbon atoms of the substituent group is not included in the number of carbon atoms in question. Suitable examples of the arylene group include a phenylene group, a naphthylene group and an anthracenylene group.

A viewpoint of realizing an insulating layer having more excellent dielectric tangent, thermal expansion rate, breaking point elongation, surface roughness and fill strength in the combination of the active ester compound (B), the thermoplastic resin (D) and the inorganic filler (E) , X is preferably an alkylene group or a cycloalkylene group, and they may have a substituent.

The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. The substituent is not particularly limited and includes, for example, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group and an acyloxy group. Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group and the alkoxy group used as a substituent may be either linear or branched and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1 to 4 , Or from 1 to 3. The number of carbon atoms of the cycloalkyl group and cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. The aryl group used as a substituent is a group excluding one hydrogen atom on an aromatic ring from an aromatic hydrocarbon and the number of carbon atoms thereof is preferably 6 to 24, more preferably 6 to 18, more preferably 6 to 14 , And more preferably 6 to 10 carbon atoms. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The acyl group used as a substituent means a group represented by the formula: -C (= O) -R ¹ (wherein R ¹ is an alkyl group or an aryl group). The alkyl group represented by R ^{1 may} be either linear or branched and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1 to 4, Or 1 to 3. The number of carbon atoms of the aryl group represented by R ¹ is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The acyloxy group used as a substituent means a group represented by the formula: -OC (= O) -R ¹ (wherein R ¹ has the same meaning as defined above). Among them, as the substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

In the general formula (2), p is an integer of 1 to 5. A viewpoint of realizing an insulating layer having more excellent dielectric tangent, thermal expansion rate, breaking point elongation, surface roughness and fill strength in the combination of the active ester compound (B), the thermoplastic resin (D) and the inorganic filler (E) , P is preferably 1 to 4, more preferably 2 to 4, still more preferably 2 or 3.

When a plurality of X's are present in the formula (2), they may be the same or different. In a suitable embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

In a preferred embodiment, the carbodiimide compound is preferably at least 50 mass%, more preferably at least 60 mass%, more preferably at least 50 mass%, more preferably at least 50 mass% Is not less than 70% by mass, more preferably not less than 80% by mass, or not less than 90% by mass, and contains the structural unit represented by the general formula (2). The carbodiimide compound may be substantially composed of the structural unit represented by the general formula (2) except for the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group and an aryl group, and they may have a substituent. The alkyl group, cycloalkyl group or aryl group used as the terminal structure is preferably an alkyl group, a cycloalkyl group or an aryl group described for the substituent which the group represented by X may have. The substituent which may be contained in the group used as the terminal structure is preferably the same as the substituent which the group represented by X may have.

From the viewpoint of suppressing the generation of outgassing at the time of curing the resin composition, the weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, more preferably 700 or more, 800 or more, particularly preferably 900 or more or 1000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5000 or less, more preferably 4500 or less, still more preferably 4000 or less, still more preferably 3500 or less It is 3000 or less. The weight average molecular weight of the carbodiimide compound can be measured by, for example, gel permeation chromatography (GPC) (in terms of polystyrene).

Further, the carbodiimide compound may originate from its production method and may contain an isocyanate group (-N = C = O) in the molecule. The content of the isocyanate group (also referred to as " NCO content ") in the carbodiimide compound is preferably 5% by mass or more, more preferably 5% by mass or less, from the viewpoint of obtaining a resin composition exhibiting good storage stability and realizing an insulating layer exhibiting desired properties. More preferably 4 mass% or less, further preferably 3 mass% or less, further preferably 2 mass% or less, particularly preferably 1 mass% or less or 0.5 mass% or less.

Commercially available products of carbodiimide compounds may be used. Examples of the commercially available carbodiimide compound include Carbodite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nissinbo Chemical Co., (Registered trademark) P, P400, and Haikasil 510, all of which are trade names.

An insulating layer excellent in dielectric tangent, thermal expansion rate, elongation at break, surface roughness and peak strength is obtained in the combination of the active ester compound (B), the thermoplastic resin (D) and the inorganic filler (E) , The content of the carbodiimide compound in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, 4% by mass or more or 5% by mass or more. The upper limit of the content of the carbodiimide compound is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

≪ (D) Thermoplastic resin >

The resin composition of the present invention comprises a thermoplastic resin as the component (D).

Examples of the thermoplastic resin include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, acid anhydride group-containing vinyl resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, styrene elastomer resin, , Polyphenylene ether resin, and polysulfone resin. The thermoplastic resin may be used singly or in combination of two or more kinds. The thermoplastic resin preferably has a glass transition temperature of 80 캜 or higher.

Among them, an insulating layer having better dielectric tangent, thermal expansion rate, breaking point elongation, surface roughness and peel strength in the combination of the active ester compound (B), the carbodiimide compound (C) and the inorganic filler (E) The thermoplastic resin is at least one selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, a vinyl resin containing an acid anhydride group, a polyimide resin, a polyamideimide resin, and a styrene-based elastomer resin .

From the viewpoint of obtaining an insulating layer having a good mechanical strength, the weight average molecular weight of the thermoplastic resin is preferably 10000 or more, more preferably 15000 or more, more preferably 20000 or more, further preferably 25000 or more, or 30000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the thermoplastic resin is preferably 200,000 or less, more preferably 180,000 or less, more preferably 160,000 or less, and still more preferably 1,500,000 or less. The weight average molecular weight of the thermoplastic resin can be measured by, for example, gel permeation chromatography (GPC). Specifically, the weight average molecular weight (in terms of polystyrene) of the thermoplastic resin was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation, Shodex K-800P / K-804L / K-804L can be measured using a calibration curve of standard polystyrene at a column temperature of 40 ° C using chloroform as the mobile phase.

(B) an active ester compound, (C) a carbodiimide compound, and (E) an inorganic filler in an amount of at least one selected from the group consisting of a dielectric tangent, a thermal expansion coefficient, a breaking point elongation, a surface roughness, From the viewpoint of obtaining an insulating layer having a high peel strength, the thermoplastic resin preferably contains at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom or a functional group containing a carbon- . Examples of the functional group include a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, a diimide group, And a ketene group. As the acid anhydride group, a carboxylic acid anhydride group is preferable. Suitable examples of the alkenyl group include a vinyl group, an allyl group and a styryl group. By using a thermoplastic resin having such a functional group, the glass transition temperature of the resulting insulating layer tends to be high, and an insulating layer exhibiting good heat resistance can be realized. When the thermoplastic resin contains such a functional group, the functional group equivalent of the thermoplastic resin is preferably 100000 or less, more preferably 90,000 or less, 80,000 or less, 70000 or less, 60000 or less, 50000 or less, 40000 or less, , 10,000 or less, 8000 or less, 6000 or less, or 5000 or less. The lower limit of the equivalent of the functional group is not particularly limited, but may be usually 50 or more, 100 or more, and the like.

Suitable thermoplastic resins will be described in more detail below, but thermoplastic resins obtained by further adding the above functional groups to the thermoplastic resins described below may be suitably used in the present invention in accordance with a known sequence.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be either a functional group of a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" (Phenoxy resin containing a bisphenol acetophenone skeleton). In addition, "FX280" and "FX293" manufactured by Shin Nitetsu Sumikin Kagaku Co., Ltd., "YL7553" and "YL7553" manufactured by Mitsubishi Kagaku Co., YL6794 "," YL7213 "," YL7290 ", and" YL7482 ".

Specific examples of the polyvinyl acetal resin include telephonic (Butyl) 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., BH series, BX series, KS series (for example, KS-1), BL series, BM series and the like.

The vinyl resin containing an acid anhydride group can be obtained, for example, by copolymerizing an acid anhydride group-containing monomer (d1) with another monomer (d2). Examples of the acid anhydride group-containing monomer (d1) include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride. The other monomer (d2) is not particularly limited as long as it can copolymerize with the acid anhydride group-containing monomer (d1), and ethylenically unsaturated monomers such as (meth) acrylic acid, (meth) acrylic acid ester and styrene may be used. Specific examples of the acid anhydride group-containing vinyl resin include "EF-30", "EF-40", "EF-60" and "EF-80" manufactured by CRAY VALLEY HSC.

Specific examples of the polyimide resin include "RIKACOAT SN-20" and "RIKACOAT PN-20" manufactured by Shin-Nihon Rika Co., Ltd., and "Unidic V-8000" manufactured by DIC Corporation. Specific examples of the polyimide resin include linear polyimide (JP-A No. 2006-37083) obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (JP-A-2006-37083), a polysiloxane skeleton- (Japanese Unexamined Patent Application, First Publication No. 2002-12667, Japanese Unexamined Patent Application, First Publication No. 2000-319386, WO 2010/53186, etc.).

Specific examples of the polyamide-imide resin include "Bioromax HR11NN" and "Bioromax HR16NN" manufactured by Toyo Boseki K.K. Specific examples of the polyamideimide resin include modified polyamideimides such as polyamideimide containing polysiloxane skeleton "KS9100" and "KS9300" manufactured by Hitachi Kasei Corporation.

As the styrene-based elastomer resin, for example, a block of styrene or its analogue is included as at least one terminal block, and an elastomer block of the conjugated diene or its hydrogenated product is included as at least one intermediate block Block copolymers. Specific examples thereof include styrene-butadiene diblock copolymers, styrene-butadiene triblock copolymers, styrene-isoprene diblock copolymers, styrene-isoprene triblock copolymers, hydrogenated styrene-butadiene diblock copolymers, Butadiene triblock copolymers, hydrogenated styrene-isoprene diblock copolymers, hydrogenated styrene-isoprene triblock copolymers, and hydrogenated styrene-butadiene random copolymers. Specific examples of the styrene-based elastomer resin include asaprene, tafu flure, asaflex manufactured by Asahi Kasei Kogyo Co., Ltd.; And a high-brass and a confounder manufactured by Kuraray Co., Ltd.

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Abbasstopolimas.

(B) an active ester compound, (C) a carbodiimide compound, and (E) an inorganic filler in an amount of at least one selected from the group consisting of a dielectric tangent, a thermal expansion coefficient, a breaking point elongation, a surface roughness, The content of the thermoplastic resin in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, further preferably 2% by mass or more. The upper limit of the content of the thermoplastic resin is not particularly limited, but is preferably 40 mass% or less, more preferably 30 mass% or less, more preferably 20 mass% or less, and further preferably 15 mass% or less.

<(E) Inorganic filler>

The resin composition of the present invention contains a certain amount or more of an inorganic filler as the component (E).

An insulating layer excellent in dielectric tangent, thermal expansion rate, breaking point elongation, surface roughness and peel strength is obtained in the combination of the active ester compound (B), the carbodiimide compound (C), and the thermoplastic resin (D) , The content of the inorganic filler in the resin composition layer is preferably not less than 40% by mass, more preferably not less than 45% by mass, more preferably not less than 50% by mass, from the viewpoint of obtaining an insulating layer with low dielectric loss tangent, , More preferably not less than 55 mass% or not less than 60 mass%. In the present invention using an inorganic filler in combination with (B) an active ester compound, (C) a carbodiimide compound and (D) a thermoplastic resin, the content of the inorganic filler . For example, the content of the inorganic filler in the resin composition may be increased to 62 mass% or more, 64 mass% or more, 66 mass% or more, 68 mass% or more, 70 mass% or more, 72 mass% or more or 74 mass% .

The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less from the viewpoint of the mechanical strength of the obtained insulating layer.

The material of the inorganic filler is not particularly limited and may be, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite , Magnesium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, Zirconium, barium titanate, barium titanate-zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphate-tungstate, and silica is particularly suitable. As the silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like can be given. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds. As commercially available spherical fused silica, "SO-C2" and "SO-C1" manufactured by Adomex Co., Ltd. can be mentioned.

The average particle diameter of the inorganic filler is not particularly limited but is preferably 3 탆 or less, more preferably 2 탆 or less, more preferably 1 탆 or less, 0.7 탆 or less from the viewpoint of obtaining an insulating layer capable of forming fine wiring thereon Mu m or less, 0.5 mu m or less, 0.4 mu m or less, or 0.3 mu m or less. On the other hand, the average particle diameter of the inorganic filler is preferably 0.01 탆 or more, more preferably 0.03 탆 or more from the viewpoint of obtaining a resin varnish having appropriate viscosity and good handling property when the resin varnish is formed using the resin composition , 0.05 탆 or more, 0.07 탆 or more, or 0.1 탆 or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured by using a laser diffraction particle size distribution measuring apparatus, and the median diameter of the inorganic filler is determined as the average particle diameter. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction particle size distribution measuring apparatus, "LA-500", "LA-750", "LA-950" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is preferably selected from the group consisting of amino silane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds and titanate coupling agents It is preferable that the surface treatment agent is treated with at least one kind of surface treatment agent. As commercially available products of the surface treatment agent, for example, KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercapto KBE903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM573 "(manufactured by Shin-Etsu Chemical Co., Methoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The degree of the surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content per unit surface area of the inorganic filler is preferably not less than 0.02 mg / m 2, more preferably not less than 0.1 mg / m 2, and most preferably not less than 0.2 mg / m 2 from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and most preferably 0.5 mg / m 2 or less from the viewpoint of preventing the melt viscosity of the resin varnish and the increase of the melt viscosity in the sheet form.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 占 폚 for 5 minutes. After the supernatant is removed and the solid content is dried, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

<(F) Curing accelerator>

The resin composition of the present invention may further contain a curing accelerator as the component (F).

Examples of the curing accelerator include, but are not limited to, amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, and guanidine-based curing accelerators. Amine-based curing accelerators and imidazole- Do. The curing accelerator may be used singly or in combination of two or more kinds.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine; amines such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) Diazabicyclo (5,4,0) undecene, and 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, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine isocyanuric acid Water, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3 -Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, And imidazole compounds of imidazole compounds and epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

Examples of phosphorus hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenyl Phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , 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-cyclohexylbiguanide, 1-arylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like can be mentioned. Amide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene are preferable.

Among them, from the viewpoint of obtaining an insulating layer having more excellent dielectric tangent, thermal expansion rate, elongation at break, surface roughness and fill strength in the combination of the above components (A) to (E), 4-dimethylaminopyridine , 1-benzyl-2-phenylimidazole are particularly preferred.

The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.005 mass% to 1 mass%, and more preferably 0.01 mass% to 0.5 mass%.

<Other components>

- hardener -

The resin composition of the present invention may further contain a curing agent (excluding the component (B)). The insulation reliability of the insulating layer obtained by containing the curing agent, the peel strength, and the mechanical strength can be increased. The curing agent is not particularly limited, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a benzoxazine-based curing agent. The curing agent may be used singly or in combination of two or more kinds. Among these, from the viewpoint of obtaining an insulating layer having better dielectric tangent, thermal expansion rate, elongation at break, surface roughness and fill strength in combination of the above components (A) to (E), a phenolic curing agent, Cyanate ester-based curing agents are preferred.

As the phenol-based curing agent and naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoints of heat resistance and water resistance. From the viewpoint of the peel strength, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Among them, a phenazine novolac resin containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with a conductor layer. Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Waxei Co., SN-180 "," SN-190 "," SN-475 "and" SN-485 "manufactured by Shinnetsu Tsushin Kagaku Co., LA-7054 "," LA-3018 "," LA-1356 "," SN-395 " &Quot; TD2090 &quot;, and the like.

The cyanate ester-based curing agent is not particularly limited, and examples thereof include cyanate ester-based curing agents, novolac-type (phenol novolac-type, alkylphenol-novolac-type and the like) cyanate ester-based curing agents, dicyclopentadiene- Cyanate ester type curing agents such as bisphenol A type, bisphenol F type, bisphenol S type and the like, and partially triarylated prepolymers thereof. Specific examples thereof include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylene bis (2,6-dimethylphenyl cyanate) , 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane) (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanate phenyl- 1- (methyl ethylidene)) benzene, bis Bifunctional cyanate resins such as bis (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolak, and prepolymers obtained by partially trimerizing these cyanate resins. Examples of commercially available cyanate ester curing agents include "PT30" and "PT60" (all phenol novolac type polyfunctional cyanate ester resins), "BA230" (a part or all of bisphenol A dicyanate And a prepolymer obtained by trimerization to form a trimer).

Specific examples of the benzoxazine type curing agent include "HFB2006M" manufactured by Showa Kobunshi Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Kasei Kogyo Co.,

The content of the curing agent in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass and more preferably 1% by mass to 6% by mass from the viewpoint of mechanical strength of the obtained insulating layer.

- Flame retardant -

The resin composition of the present invention may further contain a flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon-based flame retardants, metal hydroxides and the like. The flame retardant may be used alone, or two or more flame retardants may be used in combination. The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 9% by mass.

- Organic filler -

The resin composition of the present invention may further comprise an organic filler. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

The rubber particles are not particularly limited as long as they are fine particles of a resin which is chemically crosslinked with a rubber-elastic resin and is insoluble in an organic solvent and made into a molten resin. For example, acrylonitrile- Butadiene rubber particles, butadiene rubber particles, acrylic rubber particles and the like. Specific examples of the rubber particles include XER-9l (manufactured by Nihon Gosei Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by Aika Kogyo Co., EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.), and the like.

The average particle diameter of the organic filler is preferably in the range of 0.005 탆 to 1 탆, more preferably in the range of 0.2 탆 to 0.6 탆. The average particle diameter of the organic filler can be measured using a dynamic light scattering method. For example, an organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size of the organic filler is measured by using a concentrated system particle diameter analyzer (FPAR-1000 manufactured by Otsuka Denshi Co., Ltd.) The distribution can be measured on the basis of mass, and the median diameter of the median diameter can be measured. The content of the organic filler in the resin composition is preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass.

The resin composition of the present invention may further contain other components as necessary. Examples of such other components include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and resin additives such as thickeners, defoaming agents, leveling agents, adhesion promoters, colorants, and curable resins .

The method for preparing the resin composition of the present invention is not particularly limited and includes, for example, a method of mixing and dispersing a compounding ingredient, if necessary, with a solvent, etc., using a rotary mixer or the like.

The resin composition of the present invention may result in a cured product of low dielectric loss tangent (insulating layer). The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described in &quot; Measurement of dielectric loss tangent &quot; Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23 占 폚 by a cavity resonator perturbation method. The dielectric loss tangent is preferably 0.010 or less, more preferably 0.009 or less, still more preferably 0.008 or less, or 0.007 or less, or 0.006 or less, from the viewpoints of prevention of heat generation at high frequencies, signal delay and signal noise reduction. The lower the lower limit of the dielectric loss tangent is, the better, but it is usually 0.001 or more.

The resin composition of the present invention may result in a cured product (insulating layer) having a low thermal expansion coefficient. The coefficient of linear thermal expansion of the cured product of the resin composition of the present invention can be measured by the method described in < Measurement of Glass Transition Temperature and Linear Thermal Expansion Coefficient &quot; Specifically, the average linear thermal expansion coefficient in the plane direction at 25 to 150 ° C can be measured by thermomechanical analysis by a tensile weighting method (tensile weighting method). The cured product of the resin composition of the present invention is preferably 40 ppm / ° C or less, more preferably 35 ppm / ° C or less, still more preferably 30 ppm / ° C or less, still more preferably 25 ppm / Lt; 0 &gt; C or less. The lower limit of the coefficient of linear thermal expansion is not particularly limited, but is usually 1 ppm / DEG C or more.

The resin composition of the present invention may result in a cured product (insulating layer) exhibiting a good breaking point elongation. The elongation at break of the cured product of the resin composition of the present invention can be measured by the method described in &quot; Measurement of elongation at break &quot; Specifically, it can be measured by a tensile test method in accordance with Japanese Industrial Standards (JIS K7127). The cured product of the resin composition of the present invention preferably has a fracture point of at least 2%, more preferably at least 2.1%, more preferably at least 2.2%, more preferably at least 2.3%, at least 2.4%, or at least 2.5% Can be expressed. The upper limit of the elongation at break is preferably 30% or less, more preferably 20% or less, further preferably 10% or less.

The resin composition of the present invention may result in a cured product (insulating layer) having a low surface roughness. The arithmetic mean roughness (Ra) of the cured product of the resin composition of the present invention can be measured by the method described in &quot; Measurement of arithmetic mean roughness (Ra) &quot; The surface of the insulating layer after the roughening treatment is required to have a small surface irregularity in terms of reducing the loss of electrical signals. Specifically, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening the surface of the insulating layer by curing the resin composition is preferably 140 nm or less, more preferably 130 nm or less, More preferably 120 nm or less, further preferably 110 nm or less, and particularly preferably 100 nm or less. The lower limit of the arithmetic mean roughness (Ra) is preferably 5 nm or more, more preferably 10 nm or more, and more preferably 15 nm or more from the viewpoint of obtaining sufficient fill strength.

The resin composition of the present invention may result in a cured product (insulating layer) having a high peel strength. The peel strength of the cured product of the resin composition of the present invention can be measured by the method described in &quot; Measurement of Peel Strength of Plated Conductor Layer &quot; Specifically, when the resin composition is cured to form an insulating layer and the conductor layer is formed by plating the surface of the insulating layer after the roughening treatment, the resultant peel strength between the conductor layer and the insulating layer obtained is 0.50 kgf / cm Or more, more preferably 0.55 kgf / cm or more, and still more preferably 0.60 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but usually it is 1.2 kgf / cm or less.

The resin composition of the present invention may also result in a cured product (insulating layer) having a high glass transition temperature (Tg). The glass transition temperature (Tg) of the cured product of the resin composition of the present invention can be measured by the method described in &quot; Measurement of breaking elongation &quot; The cured product of the resin composition of the present invention preferably exhibits a glass transition temperature (Tg) of 165 DEG C or higher, more preferably 170 DEG C or higher, 175 DEG C or higher, or 180 DEG C or higher. The upper limit of the glass transition temperature (Tg) is not particularly limited, but is usually 250 DEG C or lower.

The resin composition of the present invention can be suitably used as a resin composition (a resin composition for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board and can be suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (A resin composition for an interlayer insulating layer of a printed wiring board on which a conductor layer is formed by plating) for forming an interlayer insulating layer in which a conductor layer is formed by plating, Can be more suitably used. The resin composition of the present invention can also be widely used for various applications such as sheet-like laminated materials such as adhesive films and prepregs, resin compositions such as solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole- Can be used.

[Adhesive film]

The resin composition of the present invention can be used in a varnish state, but it is generally industrially preferable to use it in the form of an adhesive film.

The adhesive film comprises a support and a resin composition layer (adhesive layer) bonded to the support, and a resin composition layer (adhesive layer) is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 100 占 퐉 or less, more preferably 80 占 퐉 or less, still more preferably 60 占 퐉 or less, further preferably 50 占 퐉 or less or 40 占 퐉 or less from the viewpoint of reducing the thickness of the printed wiring board . The lower limit of the thickness of the resin composition layer is not particularly limited, but is usually 5 占 퐉 or more or 10 占 퐉 or more.

As the support, for example, a film made of a plastic material, a metal foil and a release paper can be mentioned, and a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN" (TAC), polyether sulfide (PES), polyether sulfide (PES), polyether sulfone (PES), polyether sulfone Polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and 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 (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) good.

The support may be subjected to a mat treatment or a corona treatment on the surface of the support on the side to be bonded with the resin composition layer. As the support, a release layer-adhered support having a release layer on the surface to be bonded to the resin composition layer may be used. As the release agent for use in the release layer of the release layer-adhered support, for example, one or more release agents selected from the group consisting of an alkyd resin, an olefin resin, a urethane resin, and a silicone resin may be mentioned. Examples of commercially available products of the release agent include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin type mold release agents.

The thickness of the support is not particularly limited, but is preferably in the range of 5 탆 to 75 탆, more preferably in the range of 10 탆 to 60 탆. When the support is a release layer-adhered support, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

The adhesive film can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, applying the resin varnish on a support using a die coater or the like, and drying the resin varnish to form a resin composition layer.

Examples of the organic solvent include 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, And aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. The organic solvent may be used singly or in combination of two or more kinds.

The drying may be carried out by a known method such as heating, hot air spraying or the like. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. For example, 30 to 60 mass% of the organic solvent is used, the resin varnish is dried at 50 to 150 DEG C for 3 to 10 minutes to form the resin composition Layer can be formed.

In the adhesive film, a protective film corresponding to the support may be further laminated on the surface of the resin composition layer not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 占 퐉 to 40 占 퐉. By laminating a protective film, it is possible to prevent adhesion and scratches of dust or the like to the surface of the resin composition layer. The adhesive film can be rolled and stored. When the adhesive film has a protective film, it can be used by peeling the protective film.

The adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board) and more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board) And can further be suitably used for a resin composition (for an interlayer insulating layer of a printed wiring board on which a conductor layer is formed by plating) for forming an interlayer insulating layer in which a conductor layer is formed by plating.

[Printed circuit board]

The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

In one embodiment, the printed wiring board of the present invention can be produced by a method including the following steps (I) and (II) using the above-mentioned adhesive film.

(I) Step of laminating an adhesive film on the inner layer substrate and bonding the resin composition layer of the adhesive film to the inner layer substrate

(II) a step of thermally curing the resin composition layer to form an insulating layer

The term &quot; inner layer substrate &quot; used in the step (I) mainly refers to a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, (Circuit) formed by patterning on one side (one side) or both sides of the circuit board. Further, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the &quot; inner layer board &quot;

The lamination of the inner layer substrate and the adhesive film can be carried out, for example, by heating and pressing an adhesive film from the support side to the inner layer substrate. Examples of the member for heating and pressing the adhesive film to the inner layer substrate (hereinafter also referred to as &quot; hot pressed member &quot;) include a heated metal plate (SUS plate or the like) or a metal roll (SUS roll) . Further, it is preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the heat-press member is not directly pressed onto the adhesive film but the adhesive film sufficiently sucks the surface unevenness of the inner-layer substrate.

The lamination of the inner layer substrate and the adhesive film may be performed by a vacuum lamination method. In the vacuum laminating method, the heat pressing temperature is preferably in the range of 60 占 폚 to 160 占 폚, more preferably 80 占 폚 to 140 占 폚, and the heat pressing pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably in a range of from 20 seconds to 400 seconds, more preferably from 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure at a pressure of 26.7 hPa or less.

The lamination can be carried out by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Mitsui Mining Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Co., Ltd., and the like can be given.

After lamination, the laminated adhesive film may be subjected to smoothing treatment under atmospheric pressure (under atmospheric pressure), for example, by pressing the hot press member from the support side. The pressing condition of the smoothing treatment can be set to the same conditions as the hot pressing conditions of the lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing process may be carried out continuously using the commercially available vacuum laminator.

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

In the step (II), the resin composition layer is thermally cured to form an insulating layer.

The thermosetting condition of the resin composition layer is not particularly limited, and a condition that is generally adopted when forming the insulating layer of the printed wiring board may be used.

For example, although the thermosetting conditions of the resin composition layer are different depending on the type of the resin composition and the like, the curing temperature is in the range of 120 캜 to 240 캜 (preferably in the range of 150 캜 to 210 캜, 190 占 폚), and the curing time may be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

The resin composition layer may be preheated to a temperature lower than the curing temperature before thermosetting the resin composition layer. For example, before the resin composition layer is thermally cured, the resin composition layer is heated at a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 110 ° C or less, more preferably 70 ° C or more and 100 ° C or less) It may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

In the production of a printed wiring board, (III) a step of piercing the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer on the surface of the insulating layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for the production of printed wiring boards. When the support is removed after the step (II), the removal of the support may be carried out between the steps (II) and (III), between the steps (III) and (IV) V).

Step (III) is a step of perforating the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out using, for example, a drill, a laser, a plasma or the like depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The order and condition of the harmonization treatment are not particularly limited, and a known order and conditions commonly used in forming the insulating layer of the printed wiring board can be employed. For example, the swelling treatment with a swelling liquid, the coarsening treatment with an oxidizing agent, and the neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer. The swelling liquid is not particularly limited, but an alkaline solution, a surfactant solution and the like can be mentioned, and an alkaline solution is preferable, and a sodium hydroxide solution and a potassium hydroxide solution are more preferable as the alkaline solution. Examples of commercially available swelling liquids include Swelling · Dip · Sucuregan P, Swelling · Dip · Sucureganus SBU manufactured by Atotech Japan Co., Ltd., and the like. The swelling treatment by the swelling liquid is not particularly limited, and can be carried out, for example, by immersing the swelling liquid at 30 占 폚 to 90 占 폚 for 1 minute to 20 minutes. The oxidizing agent is not particularly limited, and examples thereof include alkaline permanganic acid solutions in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 占 폚 to 80 占 폚 for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and Dozing Solution and Sucuregan P, etc. The neutralization solution is preferably an acidic aqueous solution, and commercially available products include, for example, Reduction Solution · Sucurentant P manufactured by Atotech Japan K.K. The treatment with the neutralizing liquid can be carried out by soaking the treated surface subjected to the roughening treatment with the oxidizing agent solution in a neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes.

Step (V) is a step of forming a conductor layer on the surface of the insulating layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises at least one metal 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 either a single metal layer or an alloy layer. Examples of the alloy layer include two or more kinds of metal alloys selected from the group (for example, nickel-chromium alloy, copper-nickel alloy, Alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or a nickel-chromium alloy, a copper-nickel alloy, An alloy layer of a copper-titanium alloy 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, 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 metals or alloys are stacked. 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.

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

The conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-custom method or a pull-to-groove method. Hereinafter, an example of forming the conductor layer by the semi-specific method is described.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

As described above, by producing the printed wiring board using the resin composition of the present invention, a printed wiring board having an insulating layer excellent in dielectric tangent, thermal expansion rate, elongation at break, surface roughness and peak strength can be advantageously manufactured can do.

[Semiconductor device]

A semiconductor device can be manufactured using the printed wiring board of the present invention. Examples of the semiconductor device include various semiconductor devices provided in electrical products (such as a computer, a mobile phone, a digital camera, and a television) and a vehicle (such as a motorcycle, a car, a train, .

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) in a conductive portion of the printed wiring board of the present invention. The term &quot; conduction site &quot; means &quot; a location where electrical signals are transmitted from the printed wiring board &quot;, and the site may be a surface or a buried site. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

The method for mounting the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can function effectively. Specifically, the method includes a wire bonding mounting method, a flip chip mounting method, a bump- A mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF), and the like. Here, the "mounting method using the bump-free build-up layer (BBUL)" is a "mounting method in which the semiconductor chip is directly buried in the concave portion of the printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board.

Example

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples. The term &quot; part &quot; means the mass part.

[Measurement method and evaluation method]

First, various measurement methods and evaluation methods will be described.

&Lt; Preparation of Sample for Measurement of Peel Strength and Arithmetic Mean Roughness (Ra Value)

(1) ground treatment of inner layer circuit board

Both surfaces of a glass fiber-based epoxy resin double-sided copper-clad laminate (thickness of copper foil of 18 mu m, substrate thickness of 0.4 mm, Panasonic Co., Ltd.) on which an inner layer circuit was formed were laminated on both surfaces of a copper foil of "CZ8101" To conduct coarsening treatment of the copper surface.

(2) lamination of an adhesive film

The adhesive films produced in the examples and the comparative examples were laminated by using a batch type vacuum pressure laminator (&quot; MVLP-500 &quot;, manufactured by Mitsui Mining Co., Ltd.) Both sides were laminated. The lamination treatment was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by pressing at 100 DEG C and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of resin composition

After laminating the adhesive film, the resin composition layer was thermally cured under the conditions of 100 占 폚 for 30 minutes and then at 180 占 폚 for 30 minutes to form an insulating layer. Thereafter, the support was peeled off to expose the insulating layer.

(4) Harmonization processing

The inner-layer circuit board having the insulating layer exposed was immersed in a swelling solution ("Swelling Dip Sekirigant P" manufactured by Atotech Japan Co., Ltd., sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether) at 60 ° C for 10 minutes , Followed by immersion for 20 minutes at 80 DEG C in an oxidizing agent ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd .; an aqueous solution having a potassium permanganate concentration of about 6 mass% and a sodium hydroxide concentration of about 4 mass%), (Reduction Solution · Sucuregent P, manufactured by Atotech Japan Co., Ltd., aqueous solution of hydroxysilamine sulfate) at 40 ° C for 5 minutes. Thereafter, it was dried at 80 DEG C for 30 minutes. The resulting substrate is referred to as &quot; evaluation substrate a &quot;.

(5) Formation of conductor layer

A conductor layer was formed on the roughened surface of the insulating layer according to the semi-specific method.

That is, the substrate after the roughening treatment was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C for 5 minutes, and immersed in an electroless copper plating solution at 25 ° C for 20 minutes. Subsequently, annealing was performed by heating at 150 占 폚 for 30 minutes, and then etching resist was formed and patterned by etching. Thereafter, copper sulfate electroplating was performed to form a conductor layer having a thickness of 30 mu m, and annealing was performed at 200 DEG C for 60 minutes. The resulting substrate is referred to as &quot; evaluation substrate b &quot;.

&Lt; Measurement of arithmetic mean roughness (Ra) >

Using a non-contact surface roughness meter (&quot; WYKO NT3300 &quot; manufactured by Vico Instruments Inc.) with respect to the evaluation substrate a, the value obtained by setting the measurement range to 121 mu m x 92 mu m by the VSI contact mode, Respectively. And the average value of 10 randomly selected points was determined.

&Lt; Measurement of Peel Strength of Plated Conductor Layer >

The peel strength of the insulating layer and the conductor layer was measured according to Japanese Industrial Standards (JIS C6481) for the evaluation board b. Specifically, a cut of a portion having a width of 10 mm and a length of 100 mm was put on a conductor layer of the evaluation board b, and one end thereof was peeled off and picked up with a collecting tool, and 35 mm was peeled in a vertical direction at a rate of 50 mm / (Kgf / cm) was measured to determine the peel strength. For the measurement, a tensile tester (&quot; AC-50C-SL &quot; manufactured by TSE Corporation) was used.

<Measurement of breaking point elongation>

The adhesive films prepared in Examples and Comparative Examples were heated at 200 占 폚 for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The resulting cured product is referred to as &quot; cured product for evaluation c &quot;. The cured product c for evaluation was subjected to a tensile test by Tenshiron universal testing machine ("RTC-1250A" manufactured by ORI-TECH Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127) .

<Measurement of Glass Transition Temperature and Line Thermal Expansion Coefficient>

The cured product c for evaluation was cut into test pieces each having a width of about 5 mm and a length of about 15 mm and thermomechanical analysis was carried out by a tensile weighting method using a thermomechanical analyzer ("Thermo Plus TMA8310" manufactured by Rigaku Corporation) Respectively. Specifically, after mounting the test piece on the thermomechanical analyzer, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature raising rate of 5 캜 / minute. In the second measurement, the glass transition temperature (Tg; 占 폚) and the average coefficient of linear thermal expansion (CTE; ppm / 占 폚) in the range from 25 占 폚 to 150 占 폚 were calculated.

&Lt; Measurement of dielectric loss tangent &

The cured product c for evaluation was cut with a test piece having a width of 2 mm and a length of 80 mm. Using the "HP8362B" manufactured by Agilent Technologies, the dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C by a cavity resonance perturbation method. The two specimens were measured and the average value was calculated.

&Lt; Example 1 >

, 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent weight: about 180), 25 parts of biphenyl type epoxy resin (NC3000L manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: 269) , 25 parts of a biscylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent weight: about 185), 25 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Kagaku KK, a mixture of MEK having a solid content of 30% (1: 1 solution) were heated and dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 15 parts of a triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50% 20 parts of an ester compound (HPC-8000-65T, manufactured by DIC Corporation, active group equivalent of about 223, and a toluene solution of a nonvolatile component of 65% by mass), 20 parts of a carbodiimide compound (V-03 manufactured by Nissinbo Chemical Co., 3 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), 10% by mass of solid content of MEK solution), 20 parts of an aminosilane-based coupling agent ( 275 parts of spherical silica (average particle diameter 0.5 mu m, manufactured by Adomex Co., Ltd., &quot; SO-C2 &quot;) surface-treated with a high-speed rotary mixer were uniformly dispersed To prepare a resin varnish.

A PET film ("AL5" manufactured by LINTEC CO., LTD., Thickness: 38 mu m) with an alkyd resin-based release layer was prepared as a support. A resin varnish was uniformly coated on the release layer of the support so that the thickness of the resin composition layer after drying was 30 占 퐉 and dried at 80 占 폚 to 120 占 폚 (average 100 占 폚) for 4 minutes to produce an adhesive film.

&Lt; Example 2 >

Except that the compounding amount of the carbodiimide compound ("V-03" manufactured by Nissinbo Chemical Co., Ltd., toluene solution of nonvolatile content of 50% by mass) was changed to 80 parts to prepare a resin varnish and an adhesive film Respectively.

&Lt; Example 3 >

The blending amount of spherical silica surface-treated with an aminosilane-based coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter 0.5 mu m, manufactured by Adomex Co., , A resin varnish and an adhesive film were produced in the same manner as in Example 1.

<Example 4>

275 parts of spherical silica (average particle diameter 0.5 탆, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with an amino silane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Except that 275 parts of spherical silica surface-treated with a coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter 0.3 mu m, "SO-C1" manufactured by Adomex Co., Ltd.) A resin varnish and an adhesive film were produced in the same manner as in Example 1.

&Lt; Example 5 >

20 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active agent equivalent approximately 223, and a toluene solution of a nonvolatile component of 65% by mass) (MEK solution having an active group equivalent of about 334 and 62 mass% of a nonvolatile component) was changed to 21 parts, a resin varnish and an adhesive film were produced in the same manner as in Example 1.

&Lt; Example 6 >

3 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), a solid content of 10 mass% in MEK solution) was added to a curing accelerator (1B2PZ manufactured by Shikoku Chemicals Inc., 1-benzyl-2-phenylimidazole, % MEK solution) was changed to 6 parts, a resin varnish and an adhesive film were produced in the same manner as in Example 1. [

&Lt; Example 7 >

20 parts of a carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., toluene solution of a nonvolatile component of 50 mass%) was added to a mixture of 20 parts of a carbodiimide compound "V-07" manufactured by Nisshinbo Chemical Co., , And 20 parts of a toluene solution of a nonvolatile component (50 mass%)) was prepared in the same manner as in Example 1, except that the resin varnish and the adhesive film were changed.

&Lt; Example 8 >

20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone in a solid content of 30 mass%) was added to a polyvinyl butyral resin (glass transition temperature: 105 ° C., Except that 40 parts of a nonvolatile component (15 parts by mass of a 1: 1 solution of ethanol and toluene) (KS-1 manufactured by Kagaku Kogyo Co., Ltd., nonvolatile component: 15 parts by mass of a 1: 1 solution of toluene) was used.

&Lt; Example 9 >

20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone in a solid content of 30% by mass) was added to an acrylic acid anhydride group-containing vinyl resin ("EF- 30 &quot;, a cyclohexanone solution having a solid content of 50%) was prepared in the same manner as in Example 1, and a resin varnish and an adhesive film were prepared.

&Lt; Example 10 >

, 20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone in a solid content of 30 mass%) was added to a polyimide resin (SN-20 manufactured by Shin- , N-methyl-2-pyrrolidone (NMP) solution having a solid content of 20%) was prepared in the same manner as in Example 1, to thereby produce a resin varnish and an adhesive film.

&Lt; Example 11 >

20 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Kagaku KK, a 1: 1 solution of MEK and cyclohexanone in a solid content of 30 mass%) were mixed with 20 parts of a polyimide resin ("Unidic V-8000" , 15 parts of a nonvolatile component (40% by mass of ethyldiglycol acetate solution)) was prepared in the same manner as in Example 1, to thereby produce a resin varnish and an adhesive film.

&Lt; Example 12 >

, 10 parts of a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: about 180), 10 parts of an alicyclic epoxy resin having an ester skeleton ("Vertical Kisaido 2021P" A resin varnish and an adhesive film were produced in the same manner as in Example 2 except that the resin varnish was changed.

&Lt; Example 13 >

, The amount of the phenol based curing agent containing triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl equivalent equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%) was changed to 5 parts and a benzoxazine type curing agent (Manufactured by Shikoku Chemical Industry Co., Ltd., &quot; Pd &quot;, manufactured by Shikoku Chemical Industry Co., Ltd., cyclohexanone solution having a solid content of 50%) was added.

&Lt; Example 14 >

20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Kagaku KK, a 1: 1 solution of MEK and cyclohexanone in a solid content of 30 mass%) was added to a siloxane skeleton-containing polyimide resin (solid content 55 mass% A resin varnish and an adhesive film were produced in the same manner as in Example 2,

[Synthesis Example 1]

A 500 mL separable flask equipped with a reflux condenser, a nitrogen inlet tube, and a stirrer was charged with 20 parts of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) , 70.5 parts of lactone, 7 parts of toluene, 61.5 parts of diaminosiloxane ("X-22-9409" manufactured by Shinetsu Kagaku Kogyo K.K., amine equivalent 665), 2,6-bis (1-hydroxy- (HFA-NAP) (7.4 parts), and the mixture was stirred at 45 ° C for 2 hours under a stream of nitrogen. Then, the temperature of the reaction solution was raised, and the condensed water was azeotropically removed with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. After confirming that a predetermined amount of water was accumulated in the water amount determining machine and that the water outflow was not observed, the temperature was further raised and the mixture was stirred at 200 DEG C for 1 hour. Thereafter, the solution was cooled and terminated to prepare a varnish containing 55 mass% of a siloxane skeleton-containing polyimide resin having a hexafluoroisopropanol group (HFA group). In this case, the content of the siloxane structure in the resin is 70.9% by mass and the HFA group equivalent is 2881 g / mo1.

&Lt; Example 15 >

10 parts of a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 180) was changed to 10 parts of a bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corp., epoxy equivalent weight: about 235) , A resin varnish and an adhesive film were produced in the same manner as in Example 1.

&Lt; Comparative Example 1 &

Except that 20 parts of a carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., toluene solution of a non-volatile component of 50 mass%) was not used .

&Lt; Comparative Example 2 &

Except that 20 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active agent equivalent of about 223, and toluene solution of the nonvolatile component of 65% by mass) was not used, A film was produced.

&Lt; Comparative Example 3 &

Except that 20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone in a solid content of 30% by mass) was not used, Respectively.

&Lt; Comparative Example 4 &

40 parts of spherical silica (average particle diameter 0.5 占 퐉, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with an amino silane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that the resin varnish was changed.

The results are shown in Table 1.

Claims (18)

(A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) an inorganic filler, wherein the content of the component (E) Is at least 40% by mass based on 100% by mass of the resin composition. The resin composition according to claim 1, wherein the weight average molecular weight of the component (D) is 10,000 to 200,000. The resin composition according to claim 1, wherein the component (D) is a thermoplastic resin having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom or a functional group containing a carbon-carbon double bond. The positive resist composition according to claim 1, wherein the component (D) is at least one compound selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, Is a thermoplastic resin having at least one functional group selected from the group consisting of a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, The resin composition according to claim 1, wherein the component (D) is at least one selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, a vinyl resin containing an acid anhydride group, a polyimide resin, a polyamideimide resin and a styrene- Or more of the thermoplastic resin. The resin composition according to claim 1, wherein the component (C) has a weight average molecular weight of 500 to 5,000. The resin composition according to claim 1, wherein the component (C) has an NCO content of 5 mass% or less. The resin composition according to claim 1, wherein the content of the component (E) is 50% by mass or more based on 100% by mass of the nonvolatile component in the resin composition. The resin composition according to claim 1, wherein the component (E) has an average particle diameter of 0.01 mu m to 3 mu m. The resin composition according to claim 1, wherein the component (E) is silica. The resin composition according to claim 1, further comprising (F) a curing accelerator. 12. The resin composition according to claim 11, wherein the component (F) is 4-dimethylaminopyridine or 1-benzyl-2-phenylimidazole. The resin composition according to claim 1, wherein the resin composition is cured to form an insulating layer, and an arithmetic mean roughness (Ra) after the surface of the insulating layer is 140 nm or less. The resin composition according to claim 1, wherein the elongation at break of the cured product of the resin composition is 2% or more. The resin composition according to claim 1, wherein the cured product of the resin composition has a glass transition temperature (Tg) of 165 ° C or higher. An adhesive film comprising a support and a layer of the resin composition according to any one of claims 1 to 15 bonded to the support. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 15. A semiconductor device comprising the printed wiring board according to claim 17.