KR20180119134A - Resin composision - Google Patents

Abstract

An object of the present invention is to provide a cured product having a 10-point average roughness (Rz) and a low coefficient of linear thermal expansion, high peel strength, and alleviated frangibleness even when an inorganic filler having a small average particle diameter or a large specific surface area is used. The resin composition comprises: (A) an epoxy resin; (B) an active ester-based curing agent; (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton; and (D) an inorganic filler having an average particle diameter of 100 nm or less.

Description

RESIN COMPOSITION [0001]

The present invention relates to a resin composition. The present invention also relates to a resin sheet containing the resin composition, a printed wiring board containing an insulating layer formed of a cured product of the resin composition, and a semiconductor device.

BACKGROUND ART [0002] 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 stacked is known. In the build-up method, generally, the insulating layer is formed by curing the resin composition. For example, Patent Document 1 discloses that an insulating layer is formed by curing a resin composition containing an epoxy resin, an active ester compound, a carbodiimide compound, a thermoplastic resin, and an inorganic filler.

Japanese Unexamined Patent Application Publication No. 2016-27097

The present inventors have made a new study on the resin composition and obtained the following findings. When a large amount of inorganic filler is contained in the resin composition, the surface area of the inorganic filler is increased and the area of the interface of the inorganic filler is also increased. As a result, it was found that the cured product of the resin composition was decomposed and the roughened surface after the roughening treatment was roughened. From the viewpoint of thinning and the like, it has been found that even when an inorganic filler having a small average particle diameter or a large specific surface area is contained in the resin composition, the surface area of the inorganic filler is large and the cured product of the resin composition is further decomposed.

Disclosed is a resin composition capable of obtaining a cured product having a 10-point average roughness (Rz) and a low coefficient of linear thermal expansion and a high fill strength even when an inorganic filler having a small average particle diameter or a large specific surface area is used; A resin sheet comprising the resin composition; A printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device.

In order to achieve the object of the present invention, the inventors of the present invention have conducted intensive studies and, as a result, have found that a thermoplastic resin containing phenoxy resin, aliphatic or the like is excellent in flexibility and easy to generate a component having high polarity such as alcohol at the time of curing, As a result, it has been found that when the roughening treatment is carried out, the 10-point average roughness (Rz) may increase. Based on these findings, the inventors of the present invention have also conducted intensive investigations. As a result of intensive studies, it has been found that, when a component (C) having a rigid and hydrophobic polycyclic aromatic hydrocarbon skeleton is contained in a resin composition, an inorganic filler having a small average particle diameter or a large specific surface area (Rz) and a coefficient of linear thermal expansion (CTE), a high fill strength and an improved curability can be obtained even when the cured product has a 10-point average roughness (Rz), thereby completing the present invention.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin,

(B) an active ester-based curing agent,

(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and

(D) an inorganic filler,

(D) has an average particle diameter of 100 nm or less.

[2] A resin composition comprising (A) an epoxy resin,

(B) an active ester-based curing agent,

(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and

(D) an inorganic filler,

(D) has a specific surface area of 15 m ² / g or more.

[3] The resin composition according to [1] or [2], wherein the polycyclic aromatic hydrocarbon skeleton is an aromatic hydrocarbon skeleton in which a 5-membered ring compound and an aromatic ring are condensed.

[4] The resin composition according to any one of [1] to [3], wherein the polycyclic aromatic hydrocarbon skeleton is at least one of an indane skeleton and a fluorene skeleton.

[5] The resin composition according to any one of [1] to [4], wherein the component (C) has a weight average molecular weight of 5000 or more.

[6] The resin composition according to any one of [1] to [5], wherein the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure.

(7) a mass ratio of a recurring unit having a polycyclic aromatic hydrocarbon skeleton to a recurring unit having an imide structure (mass of recurring unit having polycyclic aromatic hydrocarbon skeleton / mass of recurring unit having imide structure) of not less than 0.5 and not more than 2 , And [6].

[8] The resin composition according to any one of [1] to [7], wherein the content of the component (C) is 0.1% by mass or more and 3% by mass or less 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 content of the component (B) is 1% by mass or more and 25% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.

[10] The resin composition according to any one of [1] to [9], wherein the content of the component (D) is 30 mass% or more and 80 mass% or less when the nonvolatile component in the resin composition is 100 mass%.

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

[12] The resin composition according to [11], wherein the (E) curing agent is a phenol-based curing agent.

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

[14] The resin composition according to any one of [1] to [13], which is used for forming an insulating layer of a printed wiring board.

[15] The resin composition according to any one of [1] to [14], which is for forming an interlayer insulating layer of a printed wiring board.

[16] A resin sheet comprising a support and a resin composition layer according to any one of [1] to [15] provided on the support.

[17] A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,

Wherein the insulating layer is 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, even when an inorganic filler having a small average particle diameter or a large specific surface area is used, it is possible to obtain a cured product having a 10-point average roughness (Rz) and a low coefficient of linear thermal expansion, ; A resin sheet comprising the resin composition; A printed wiring board having an insulating layer formed using the resin composition, and a semiconductor device.

1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

Hereinafter, the resin composition, resin sheet, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Resin composition]

A resin composition according to a first embodiment of the present invention is a resin composition comprising (A) an epoxy resin, (B) an active ester curing agent, (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) (D) has an average particle diameter of 100 nm or less. The resin composition of the second embodiment of the present invention is a resin composition comprising (A) an epoxy resin, (B) an active ester curing agent, (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) , And the specific surface area of the component (D) is not less than 15 m ² / g. The resin composition of the first embodiment contains (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, (D) even when an inorganic filler having an average particle diameter of 100 nm or less is contained, the 10-point average roughness (Rz) It is possible to obtain a resin composition capable of obtaining a cured product having a low coefficient, high peel strength, and improved driability. Likewise, the resin composition of the second embodiment contains (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) even if an inorganic filler having a specific surface area of 15 m ² / g or more is contained, the 10 point average roughness ) And a resin composition capable of obtaining a cured product having a low coefficient of linear thermal expansion, high peel strength and improved drift can be obtained.

The resin composition may further contain components such as (E) a curing agent (excluding the active ester type curing agent), (F) a curing accelerator, (G) a thermoplastic resin, and (H) . Hereinafter, each component contained in the resin composition of the first and second embodiments of the present invention will be described in detail. Here, the resin composition of the first embodiment and the resin composition of the second embodiment may be collectively referred to as " resin composition ".

≪ (A) Epoxy resin >

The resin composition comprises (A) an epoxy resin. Examples of the epoxy resin include epoxy resins such as biquicylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, A naphthalene type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl type epoxy resin, Alicyclic epoxy resin, cycloaliphatic epoxy resin, spiro-ring-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexane-type epoxy resin, Epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, Trimethylol-type epoxy resins, and tetraphenylethanepolyoxy resins. The epoxy resins may be used alone or in combination of two or more.

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, the resin composition includes a combination of an epoxy resin (hereinafter referred to as a " liquid epoxy resin ") that is liquid at a temperature of 20 캜 and an epoxy resin that is solid at 20 캜 (hereinafter also referred to as " solid epoxy resin & . As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable. As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable. In the present invention, an aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

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, glycidylamine type epoxy resin, phenol novolak type epoxy resin , An alicyclic epoxy resin having an ester skeleton, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a glycidylamine-type epoxy resin, and an epoxy resin having a butadiene structure are preferable. Bisphenol A type epoxy resins, F type epoxy resin and cyclohexane type epoxy resin are more preferable, and a bisphenol A type epoxy resin is more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL", "825", "Epikote 828EL (Bisphenol A type epoxy resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin) "630" ZX1059 " (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumikinka Chemical Co., and EX-721 (a glycidyl ester type epoxy resin (Alicyclic epoxy resin having an ester skeleton), " PB-3600 " (epoxy resin having a butadiene structure), " ZX1658 ", " ZX1658GS (Liquid 1,4-glycidyl cyclohexane type epoxy resin ), Mitsubishi car "630LSD" (glycidyl amine-type epoxy resin of the flexors, Ltd.) and the like. These may be used alone, or two or more kinds may be used in combination.

Examples of the solid epoxy resin include epoxy resins such as bicalcylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, Epoxy resins such as phenylene type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin and tetraphenyl ethane type epoxy resin are preferable, and biscylenol type epoxy resin, More preferably a bisphenol AF type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin and a naphthylene ether type epoxy resin, and more preferably a biquilene type epoxy resin, a naphthol type epoxy resin and a biphenyl type epoxy resin. Specific examples of the solid epoxy resin include HP4032H (naphthalene type epoxy resin), HP-4700, HP-4710 (naphthalene type tetrafunctional epoxy resin), N-690 HP-7200H "," HP-7200H "," EXA-7311 "(dicyclopentadiene type epoxy resin)," N-695 "(cresol novolak type epoxy resin) EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)" EPPN-502H "(manufactured by Nippon Kayaku Co., Quot; NC3000L ", " NC3100L ", " NC3100 " (biphenyl type epoxy resin), " NC7000L " (naphthol novolak type epoxy resin) ESN475V "(naphthalene type epoxy resin)," ESN485 "(naphthol novolak type epoxy resin)," YX4000H "," YX4000 ", and" YL6121 "manufactured by Mitsubishi Kagaku ), "YX4000HK" (biquileneol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" manufactured by Mitsubishi Kagaku Co., Quot; jER1010 " (solid bisphenol A type epoxy resin) and " jER1031S " (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Kagaku Co., have. These may be used alone, or two or more kinds may be used in combination.

When the liquid epoxy resin and the solid epoxy resin are used in combination as the component (A), their ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1:20 in terms of the mass ratio. By setting the proportions of the liquid epoxy resin and the solid epoxy resin within this range, it is possible to obtain appropriate flexibility when i) the resin is used in the form of a resin sheet, and ii) when it is used in the form of a resin sheet, 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) in the mass ratio is more preferably in the range of 1: 0.3 to 1:10, 0.5 to 1: 1.5 is more preferable.

The content of the component (A) in the resin composition is preferably 15% by mass or more, more preferably 15% by mass or more, more preferably 15% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability By mass or more, and more preferably 25% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 60 mass% or less, more preferably 45 mass% or less, 40 mass% or less, or 35 mass% or less.

The epoxy equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. By such a 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 an epoxy group.

The weight average molecular weight of the component (A) 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-based curing agent>

The resin composition includes (B) an active ester-based curing agent. The active ester-based curing agent is an active ester compound having at least one active ester group in one molecule. As the active ester-based curing agent, an active ester-based curing agent having two or more active ester groups per molecule is preferable, and examples thereof include phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compounds Of an ester group-containing curing agent having two or more ester groups having a high reaction activity such as esters. The active ester type curing agents may be used singly or in combination of two or more kinds.

From the viewpoint of improving heat resistance, an active ester-based curing agent 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 curing agent 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 a carboxylic acid compound is reacted with an aromatic compound having a phenolic hydroxyl group to obtain More preferably an aromatic compound having at least two active ester groups in a molecule and an aromatic compound obtained by reacting a carboxylic acid compound having at least two or more carboxyl groups in one molecule with an aromatic compound having a phenolic hydroxyl group, Even more preferred are aromatic compounds having at least two active ester groups in the molecule. The active ester-based curing agent 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 an aliphatic carboxylic acid having 1 to 20 carbon atoms and an aromatic carboxylic acid having 7 to 20 carbon atoms. The aliphatic carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 8 carbon atoms. Specific examples thereof include acetic acid, malonic acid, succinic acid, Itaconic acid and the like. The aromatic carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 7 to 10 carbon atoms, and specifically includes benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. 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.

The phenol compound preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, more preferably 6 to 23 carbon atoms, and more preferably 6 to 22 carbon atoms Do. Suitable specific examples of the phenol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, dihydroxybenzophenone, 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.

The naphthol compound preferably has 10 to 40 carbon atoms, more preferably 10 to 30 carbon atoms, and more preferably 10 to 20 carbon atoms. Suitable specific examples of the naphthol compound include? -Naphthol,? -Naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. 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, alpha -naphthol, beta -naphthol, 1,5- dihydroxynaphthalene, Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol, phenol novolac, And phosphorus atom-containing oligomers having a phenolic hydroxyl group are preferable, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Containing oligomers having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, - dihydroxyl Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, phenol novolac, And phosphorus atom-containing oligomers having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene- Phenol novolac 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 diphenol, phosphorus atom-containing oligomers having a phenolic hydroxyl group are particularly preferable, and dicyclopentadiene type diphenyl is particularly preferable.

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

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

As the active ester-based curing agent, the active ester-based curing agents disclosed in JP-A-2004-277460 and JP-A-2013-40270 may be used, or a commercially available active ester-based curing agent may be used . EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000L-65M "(dicyclopentadiene type di Quot; EXB9416-70BK &quot; (active ester type curing agent containing a naphthalene structure) manufactured by DIC Corporation, &quot; DC808 &quot; (including acetylated phenol novolak manufactured by Mitsubishi Kagaku Co., EXB9050L-62M &quot; (phosphorus atom-containing active ester-based curing agent) manufactured by DIC Co., Ltd.) as the curing accelerator for active ester based curing agent, YLH1026 (active ester curing agent containing phenol novolak benzoylate) manufactured by Mitsubishi Kagaku Co., .

The content of the active ester-based curing agent is preferably 1% by mass or more, more preferably 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of lowering the linear thermal expansion coefficient and increasing the peel strength And more preferably 10% by mass or more. The upper limit of the content of the active ester-based curing agent is not particularly limited, but is preferably 25 mass% or less, more preferably 20 mass% or less, still more preferably 15 mass% or less.

When the number of epoxy groups in the epoxy resin (A) is 1, the number of reactors of the active ester curing agent (B) is preferably 0.1 to 10, more preferably 0.1 to 5, in view of obtaining an insulating layer having a good mechanical strength More preferably from 0.1 to 1, and still more preferably from 0.1 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 the epoxy resins. The term &quot; reactor &quot; means a functional group capable of reacting with an epoxy group. The term &quot; reactor number of active ester-based curing agent &quot; means the sum of values obtained by dividing the solid content of active ester- Value.

&Lt; Polyimide resin having polycyclic aromatic hydrocarbon skeleton (C) >

The resin composition comprises (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton. By using an inorganic filler having a small average particle diameter or a large specific surface area by having a rigid skeleton, a polycyclic aromatic hydrocarbon skeleton, a 10-point mean roughness (Rz) and a low coefficient of linear thermal expansion are obtained, can do. As described above, the thermoplastic resin containing phenoxy resin, aliphatic or the like has a high polarity, and therefore the resistance to demerit is low, and as a result, the 10-point average roughness (Rz) may be increased. The component (C) has a rigid imide resin and a polycyclic aromatic hydrocarbon skeleton which is rigid and has a good hydrophobic structure. The cured product of the resin composition containing the component (C) has a lower polarity than that of a thermoplastic resin such as a phenoxy resin, and as a result, the roughness after the roughening treatment can be lowered so that the 10-point average roughness (Rz) Can be lowered. Further, since the component (C) has a rigid skeleton, the resin is hardly broken, and therefore, the peel strength is increased. Further, since the component (C) has a rigid skeleton and is therefore difficult to expand, it is considered that the coefficient of linear thermal expansion is lowered.

The polycyclic aromatic hydrocarbon refers to a hydrocarbon having two or more cyclic structures in one molecule and at least one of the cyclic structures is an aromatic ring, and two or more cyclic structures may be condensed or not condensed.

The polycyclic aromatic hydrocarbon skeleton may have no substituent or may have a substituent. Substituent is not particularly limited, for example, a halogen atom, -OH, -OC _1-6 alkyl, -N (C _1-6 alkyl) _2, C _1-6 alkyl, C _6-10 aryl groups, -NH ₂ , -CN, -C (O) OC _1-6 alkyl group, -COOH, -C (O) H, -NO ₂ , and the like, and more preferably a C _1-6 alkyl group. The substituent may be either one kind or a plurality of substituents.

Here, the term "C _p-q " (p and q are positive integers, and p <q is satisfied) indicates that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, "C _{1 - 6} alkyl group" term represents an alkyl group of 1 to 6 carbon atoms.

Examples of the polycyclic aromatic hydrocarbon skeleton include an aromatic hydrocarbon skeleton condensed with an aromatic ring and a 5-membered ring compound such as an indane skeleton including a 1,1,3-trimethylindane skeleton and a fluorene skeleton; An aromatic hydrocarbon skeleton condensed with an aromatic group such as a naphthalene skeleton and an anthracene skeleton; And an aromatic hydrocarbon skeleton (non-condensed aromatic hydrocarbon skeleton) in which two or more aromatic groups such as a biphenyl skeleton are not condensed. From the viewpoint of lowering the 10-point average roughness (Rz), the 5-membered ring compound and the aromatic ring are condensed Aromatic hydrocarbon skeleton is preferred. Among them, the polycyclic aromatic hydrocarbon skeleton is preferably at least one of an indane skeleton and a fluorene skeleton from the viewpoint of lowering the linear thermal expansion coefficient of the cured product of the resin composition and increasing the glass transition temperature and the fill strength.

(C) is not particularly limited as long as it is an imide resin having a polycyclic aromatic hydrocarbon skeleton. From the viewpoint of lowering the coefficient of linear thermal expansion of the cured product of the resin composition and increasing the glass transition temperature and the peel strength, the cyclic imide structure Is preferably a polyimide resin.

Examples of the cyclic imide structure include phthalimide, succinimide, glutarimide, 3-methylglutarimide, maleimide, dimethylmaleimide, trimellitimide, pyromellitimide, May be phthalimide or succinimide. Among them, a polyimide resin having an aromatic imide structure is preferable, and phthalimide is more preferable.

From the viewpoint of lowering the coefficient of linear thermal expansion of the cured product of the resin composition and increasing the glass transition temperature and the peel strength, the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure desirable.

As the repeating unit having a polycyclic aromatic hydrocarbon skeleton, for example, a repeating unit represented by the following formula (1) is preferable.

[Chemical Formula 1]

(Wherein A represents a polycyclic aromatic hydrocarbon skeleton and D represents a single bond or a divalent linking group)

A in the general formula (1) represents a polycyclic aromatic hydrocarbon skeleton, and details of the polycyclic aromatic hydrocarbon skeleton are as described above.

D in the general formula (1) represents a single bond or a divalent linking group, and a divalent linking group is preferable. Examples of the divalent linking group include a group consisting of an oxygen atom, a sulfur atom, an alkylene group, an arylene group, -NH-, -C (= O) -, -SO-, .

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group, and a methylene group is preferable.

The arylene group is preferably an arylene group having 6 to 14 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group and an anthracenylene group, and a phenylene group is preferable.

The alkylene group and the arylene group may have no substituent or may have a substituent. The substituent is the same as the substituent which may have a polycyclic aromatic hydrocarbon skeleton.

The group formed by combining two or more of them is preferably a group formed by combining two or more of oxygen atom, arylene group, and alkylene group. Examples of such groups include groups in which at least one arylene group and at least one alkylene group are bonded (a group formed by a combination of an arylene group and an alkylene group), a group in which at least one oxygen atom is combined with at least one arylene group An oxygen atom and an arylene group), and the like. Examples of the group in which at least one arylene group and at least one alkylene group are bonded include a bivalent group comprising phenylene-methylene and a bivalent group comprising phenylene-dimethylmethylene. Examples of the group in which at least one oxygen atom and at least one arylene group are bonded include a divalent group consisting of a phenylene-oxygen atom-phenylene group, a divalent group composed of an oxygen atom-phenylene group, an oxygen atom-naphthalene group And the like.

Suitable examples of the repeating unit having a polycyclic aromatic hydrocarbon skeleton include the following.

The repeating unit having an imide structure is not particularly limited as long as it has an imide structure. From the viewpoint of lowering the linear thermal expansion coefficient of the cured product of the resin composition and increasing the glass transition temperature and the peel strength, the repeating unit having a cyclic imide structure Unit.

Examples of the cyclic imide structure include phthalimide, succinimide, glutarimide, 3-methylglutarimide, maleimide, dimethylmaleimide, trimellitimide, pyromellitimide, Phthalimide, and succinimide. Of these, an aromatic imide structure is preferable, and phthalimide is more preferable. The repeating unit having an imide structure may be a form in which the above-mentioned imide structure is combined with a divalent linking group. The divalent linking group is the same as the divalent linking group represented by D in formula (1).

Suitable examples of the repeating unit having an imide structure include the following.

The mass ratio (mass of the repeating unit having a polycyclic aromatic hydrocarbon skeleton / mass of the repeating unit having an imide structure) of the repeating unit having a polycyclic aromatic hydrocarbon skeleton and the repeating unit having an imide structure is preferably 0.5 or more More preferably not less than 0.6, further preferably not less than 0.8, preferably not more than 2, more preferably not more than 1.8, further preferably not more than 1.5. By making the mass ratio fall within this range, it becomes possible to lower the coefficient of linear thermal expansion of the cured product of the resin composition and to increase the glass transition temperature and the peel strength.

The method for producing the component (C) is not particularly limited, and can be produced by various methods. As a suitable embodiment, polymerization can be carried out by using a monomer as a repeating unit having an imide structure and a monomer as a repeating unit having a polycyclic aromatic hydrocarbon skeleton. When polymerization is carried out, a polymerization initiator or the like may be used if necessary.

The weight average molecular weight of the component (C) is preferably 5000 or more, more preferably 10000 or more, still more preferably 100 or more, from the viewpoint of obtaining a cured product having a 10-point average roughness (Rz) and a low coefficient of linear thermal expansion Is preferably 11000 or more, preferably 100000 or less, more preferably 50,000 or less, further preferably 30,000 or less. Here, the weight average molecular weight of the component (C) is the weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

From the viewpoint of obtaining a cured product having a low 10-point average roughness (Rz) and a low coefficient of linear thermal expansion and a high fill strength, the content of the component (C) is preferably 100% by mass or less, 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more. The upper limit is preferably 3 mass% or less, more preferably 2 mass% or less, and further preferably 1.5 mass% or less.

<(D) Inorganic filler>

The resin composition of the first embodiment includes (D) an inorganic filler having an average particle diameter of 100 nm or less. The resin composition of the second embodiment includes (D) an inorganic filler having a specific surface area of 15 m ² / g or more. The material of the component (D) is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Magnesium oxide, magnesium oxide, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, Barium titanate, barium titanate-barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium-tungstate phosphate. Of these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler in the first embodiment is 100 nm or less, preferably 90 nm or less, and more preferably 80 nm or less from the viewpoint of thinning and lowering the 10-point average roughness (Rz). The lower limit of the average particle diameter is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.

The average particle diameter of the inorganic filler in the second embodiment is preferably 100 nm or less, more preferably 90 nm or less, still more preferably 90 nm or less, from the viewpoint of thinning and lowering the 10-point average roughness (Rz) 80 nm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.

Examples of commercially available inorganic fillers having such an average particle diameter include &quot; UFP-30 &quot; manufactured by Denki Kagaku Kogyo Co., Ltd. and the like.

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 with a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is determined as the average particle diameter. The sample to be measured is preferably an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd., "SALD-2200" manufactured by Shimadzu Corporation can be used.

The specific surface area of the inorganic filler in the second embodiment is preferably not less than 15 m ² / g, more preferably not less than 20 m ² / g, and still more preferably not less than 20 m ² / g, from the viewpoint of thinning and lowering the 10-point average roughness (Rz) 30 m ² / g or more. The upper limit is not particularly limited, but is preferably 60 m ² / g or less, more preferably 50 m ² / g or less, and still more preferably 40 m ² / g or less.

The specific surface area of the inorganic filler in the first embodiment is preferably not less than 15 m ² / g, more preferably not less than 20 m ² / g, and more preferably not less than 20 m ² / g, from the viewpoint of thinning and lowering of the 10-point average roughness (Rz) More preferably 30 m ² / g or more. The upper limit is not particularly limited, but is preferably 60 m ² / g or less, more preferably 50 m ² / g or less, and still more preferably 40 m ² / g or less.

The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountain Tex) according to the BET method, and calculating the specific surface area using the BET multi-point method.

From the viewpoint of enhancing the moisture resistance and dispersibility, the inorganic filler is preferably a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, , Titanate-based coupling agents, and the like, and more preferably those treated with an aminosilane-based silane coupling agent. Examples of commercial products of surface treatment agents include KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercaptopropyltrimethoxy Silane), KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin- KBM103 "(phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM-4803 "manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy-type silane couples , KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

From the viewpoint of improving the dispersibility of the inorganic filler, the surface treatment by the surface treatment agent is preferably surface-treated with 0.2 to 5 parts by mass of the surface treating agent per 100 parts by mass of the component (D), preferably 0.2 part by mass To 4 parts by mass, more preferably 0.3 part by mass to 3 parts by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Suitable amount of the carbon surface unit of the inorganic filler is from the point of view of improving the dispersibility of the inorganic filler, 0.02mg / m ² or more is preferable, and, 0.1mg / m ² or more is more preferable, 0.2mg / m ² or more is more preferred . On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity of the sheet form, 1mg / m ² or less are preferred, 0.8mg / m ² or less, more preferably, 0.5mg / m ² or less, more desirable.

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.

The content of the component (D) is preferably not less than 30% by mass, more preferably not less than 35% by mass, more preferably not less than 30% by mass, more preferably not less than 30% Is at least 40% by mass. The upper limit is preferably 80 mass% or less, more preferably 70 mass% or less, further preferably 65 mass% or less, from the viewpoint of improving the insulating performance.

<(E) Curing agent>

In one embodiment, the resin composition may contain (E) a curing agent. However, the (E) curing agent referred to herein does not include the active ester curing agent (B). The component (E) is not particularly limited as long as it has a function of curing the component (A), and examples thereof include a phenol series curing agent, a naphthol series curing agent, a benzoxazine series curing agent, a cyanate ester series curing agent and a carbodiimide series curing agent And the like. Among them, as the component (E), a phenol-based curing agent is preferable. The curing agent may be used alone or in combination of two or more.

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 adhesion with the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a phenazine-based curing agent containing a triazine skeleton is more preferable.

Specific examples of the phenol-based curing agent and naphthol-based curing agent include MEH-7700, MEH-7810 and MEH-7851 manufactured by Meiwa Kasei Co., Ltd., NHN manufactured by Nippon Kayaku Co., SN375 "," SN-495V "," SN375 "," SN395 "," SN375 "," TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "and" EXB-9500 "manufactured by DIC Corporation.

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

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins derived from phenolic novolacs and cresol novolacs such as bis (4-cyanophenyl) thioether and bis (4-cyanate phenyl) ether, and polyfunctional cyanate resins derived from these cyanate resins, And prepolymers. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (multifunctional cyanate ester resin), "BA230 BA230S75 &quot; (a prepolymer obtained by trimerizing a part or all of bisphenol A dicyanate to form a trimer), and the like.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co.,

When the resin composition contains the component (E), the ratio of the amount of the component (A) to the amount of the component (E) is the ratio of [the total number of epoxy groups in component (A)]: , Preferably in the range of 1: 0.01 to 1: 2, more preferably 1: 0.05 to 1: 1.5, and even more preferably 1: 0.08 to 1: 1. Here, the reactor of the component (E) is an active hydroxyl group or the like and varies depending on the kind of the component (E). The total number of epoxy groups in the component (A) refers to a value obtained by dividing the solid component mass of each component (A) by the epoxy equivalent, relative to all the component (A), and the total number of reactors of the component , And the value obtained by dividing the solid mass of each component (E) by the equivalent of the reactor is calculated for all the (E) components. By setting the proportions of the component (A) and the component (E) to such a range, the coefficient of linear thermal expansion of the cured product of the resin composition can be lowered, and the peel strength can be further improved.

When the resin composition contains the component (E), the ratio of the epoxy resin to the component (B) and the component (E) is the total number of the epoxy groups of the component (A) Is preferably in the range of 1: 0.01 to 1: 3, more preferably 1: 0.005 to 1: 2, and more preferably 1: 0.1 to 1: 1.5, in the ratio of the total number of the reactors of the component More preferable.

When the resin composition contains the component (E), the content of the component (E) is preferably 100% by mass or less, more preferably 100% by mass or less, from the viewpoint of lowering the linear thermal expansion coefficient of the cured product of the resin composition, , It is preferably not more than 15 mass%, more preferably not more than 10 mass%, further preferably not more than 5 mass%. The lower limit is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more.

<(F) Curing accelerator>

In one embodiment, the resin composition may contain (F) a curing accelerator. Examples of the curing accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators and metal hardening accelerators. Phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, Accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators are more preferable. The curing accelerator may be used singly or in combination of two or more.

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 amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 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 preferred.

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- , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline An imidazole compound and an adduct of an imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used. Examples thereof include &quot; P200-H50 &quot; manufactured by Mitsubishi Kagaku Co.,

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] 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene are preferred.

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

When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.05% by mass or more, 0.1% by mass or more. The upper limit is preferably 3 mass% or less, more preferably 2 mass% or less, further preferably 1 mass% or less. When the content of the curing accelerator is within this range, a cured product of the resin composition having a low coefficient of linear thermal expansion and high peel strength can be obtained.

&Lt; (G) Thermoplastic resin >

In one embodiment, the resin composition may contain (G) a thermoplastic resin. However, the (G) thermoplastic resin referred to herein does not include a polyimide resin having (C) a polycyclic aromatic hydrocarbon.

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin (except for polyimide resin corresponding to component (C)), polyamideimide resin, A polyether imide resin, a polyether imide resin, a polysulfone resin, a polyether sulfone resin, a polyphenylene ether resin, a polycarbonate resin, a polyether ether ketone resin, a polyester resin and the like, and phenoxy resin is preferable. The thermoplastic resins may be used alone or in combination of two or more.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably 8,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, particularly preferably 40,000 or more. The upper limit is not particularly limited, but is preferably 70,000 or less, and more preferably 60,000 or less. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation, Shodex K-800P / K-804L / K- 804L as a mobile phase, chloroform at a column temperature of 40 占 폚, and using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac 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 any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resins may be used alone or in combination of two or more. 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" Phenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Shin Nitetsu Sumikinka Chemical Co., Ltd., "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Kagaku Co., YL7769BH30 "," YL6794 "," YL7213 "," YL7290 ", and" YL7482 ".

Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, "DENKI (electrification) butyral 4000-2", "DENKYBUTYRAL 5000-A", "DENKYBUTYRAL 6000-C", " (E.g., BK-5Z), KS series (e.g. KS-1), BL series, BM series, etc., manufactured by Sekisui Chemical Co., .

Specific examples of the polyimide resin include "Rika coat SN20" and "Rika coat PN20" manufactured by Shin-Nihon Chemical Co., Ltd. Specific examples of the polyimide resin include a linear polyimide (polyimide described in JP-A 2006-37083) obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, Modified polyimides such as polysiloxane skeleton-containing polyimide (Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.).

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include an oligophenylene ether styrene resin "OPE-2St 1200" having a vinyl group manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 0.3% by mass or more, 0.5% by mass or more. The upper limit is preferably 10 mass% or less, more preferably 5 mass% or less, still more preferably 3 mass%.

<(H) Other additives>

In one embodiment, the resin composition may further contain other additives as required. Examples of the other additives include organic phosphorus compounds, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon compounds, metal hydroxides and the like Flame retardant; Organic fillers such as rubber particles; Organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; A thickening agent, a defoaming agent, a leveling agent, an adhesion-imparting agent, and a coloring agent.

&Lt; Physical properties and uses of resin composition >

The resin composition of the present invention results in an insulating layer (cured resin composition layer) having a low ten point average roughness (Rz) and a coefficient of linear thermal expansion after roughening treatment and a high peel strength. Therefore, the resin composition of the present invention can be suitably used as a resin composition layer for insulation purposes. Specifically, 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 a resin composition for forming an interlayer insulating layer of a printed wiring board (A resin composition for an interlaminar insulating layer of a printed wiring board). In addition, the resin composition of the present invention can be suitably used even in the case where the printed wiring board is a component built-in circuit board, because it results in an insulating layer having a good part filling property. Further, the resin composition of the present invention is suitable as a resin composition (a resin composition for forming an insulating layer for forming a conductor layer) for forming the insulating layer for forming a conductor layer (including a rewiring layer) on an insulating layer Can be used.

The cured product obtained by thermosetting the resin composition at 100 占 폚 for 30 minutes and then at 180 占 폚 for 30 minutes shows a characteristic that the ten-point average roughness (Rz) after the roughening treatment is low. That is, the 10-point average roughness results in a lower insulating layer. The 10-point average roughness (Rz) is preferably 1500 nm or less, more preferably 1000 nm or less, and further preferably 600 nm or less. The lower limit is not particularly limited, but may be 1 nm or more. The measurement of the ten-point average roughness (Rz) can be carried out according to the description method of &quot; Measurement of Peel Strength, 10-point Average Roughness (Rz Value) &quot;

The cured product obtained by thermosetting the resin composition at 100 占 폚 for 30 minutes and then at 180 占 폚 for 30 minutes exhibits a high fill strength (plated fill strength). That is, it results in an insulating layer having a high peel strength. The fill strength is preferably at least 145 kgf / cm, more preferably at least 148 kgf / cm, and even more preferably at least 150 kgf / cm. The upper limit is not particularly limited, but may be 300 kgf / cm or less. The measurement of the peel strength can be performed according to the description method of &quot; Measurement of Peel Strength, 10-point Average Roughness (Rz Value) &quot;

The cured product obtained by thermosetting the resin composition at 200 占 폚 for 90 minutes exhibits a high glass transition temperature. Thus, the smoothing results in an improved insulating layer. The glass transition temperature is preferably 145 占 폚 or higher, more preferably 148 占 폚 or higher, even more preferably 150 占 폚 or higher. The upper limit is not particularly limited, but may be 300 deg. C or lower. The glass transition temperature can be measured according to the description method of &quot; Measurement of Glass Transition Temperature and Linear Thermal Expansion Coefficient &quot;

The cured product obtained by thermosetting the resin composition at 200 占 폚 for 90 minutes exhibits a low coefficient of linear thermal expansion. That is, it results in an insulating layer having a low coefficient of linear thermal expansion. The linear thermal expansion coefficient is preferably 45 ppm or less, more preferably 44 ppm or less, and further preferably 43 ppm or less. The lower limit is not particularly limited, but may be 1 ppm or more. Measurement of the coefficient of linear thermal expansion can be performed according to the description method of &quot; Measurement of Glass Transition Temperature and Linear Thermal Expansion Coefficient &quot;

[Resin sheet]

The resin sheet of the present invention comprises a support and a resin composition layer formed on the support and formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 200 占 퐉 or less, more preferably 100 占 퐉 or less, still more preferably 50 占 퐉 or less, still more preferably 20 占 퐉 or less, 15 占 퐉 or less, Or 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 占 퐉 or more, 3 占 퐉 or more, and the like.

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 may be abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN" (TAC), polyether sulfide (PES), and the like, such as polyester, polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethylmethacrylate (PMMA) ), Polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used 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 copper alloy metal 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.) may be used.

The support may be subjected to a matting treatment, a corona treatment, and an antistatic treatment on the surface to be bonded to the resin composition layer.

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the release layer-adherend support include at least one release agent selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. SK-1 &quot;, &quot; AL-5 &quot;, and &quot; AL-5 &quot;, manufactured by Lintec Corporation, which is a PET film having a release layer composed mainly of an alkyd resin releasing agent as a main component, 7, &quot; Lumirror T60 &quot; manufactured by Toray Industries, Inc., &quot; Purex &quot; manufactured by Dejin Corporation, and Unipyl manufactured by Uniqica Corporation.

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 release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

In one embodiment, the resin sheet may further include other layers as required. Examples of such other layers include a protective film based on a support provided 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 m to 40 m. By laminating a protective film, it is possible to suppress adhesion and scratches of dust or the like on the surface of the resin composition layer.

The resin sheet can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, coating 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, Carbitol such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvents may be used alone, or two or more kinds may be used in combination.

The drying may be carried out by a known method such as heating or hot air spraying. 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% by mass, is used, the resin varnish is dried at 50 to 150 캜 for 3 minutes to 10 minutes, whereby the resin composition Layer can be formed.

The resin sheet can be rolled and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[Printed circuit board]

The printed wiring board of the present invention comprises an insulating layer, a first conductor layer, and a second conductor layer formed by a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer to insulate the first conductor layer from the second conductor layer (the conductor layer may be referred to as a wiring layer).

The thickness of the insulating layer between the first and second conductor layers is preferably 6 占 퐉 or less, more preferably 5.5 占 퐉 or less, and still more preferably 5 占 퐉 or less. The lower limit is not particularly limited, but may be 0.1 탆 or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) is, as shown in an example in Fig. 1, the distance between the major surface 11 of the first conductor layer 1 Refers to the thickness t1 of the insulating layer 3 between the main surfaces 21 of the second conductor layer 2. [ The first and second conductor layers are adjacent conductor layers through the insulating layer, and the main surface 11 and the main surface 21 are opposed to each other.

The total thickness t2 of the insulating layer is preferably 15 mu m or less, more preferably 13 mu m or less, and further preferably 10 mu m or less. The lower limit is not particularly limited, but may be usually 1 占 퐉 or more, 1.5 占 퐉 or more, 2 占 퐉 or more, or the like.

The printed wiring board can be produced by a method including the following steps (I) and (II) using the resin sheet described above.

(I) a step of laminating a resin composition layer of a resin sheet to be laminated on an inner layer substrate on an inner layer substrate

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

The &quot; inner layer substrate &quot; used in the step (I) is a member which becomes a substrate of a printed wiring board, and examples thereof include glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, Ether substrates and the like. The substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner-layer substrate on which a conductor layer (circuit) is formed on one or both surfaces of the substrate is sometimes referred to as an &quot; inner-layer circuit substrate &quot;. Further, in manufacturing a printed wiring board, an intermediate product to be formed with an insulating layer and / or a conductor layer is also included in the &quot; inner layer substrate &quot; When the printed wiring board is a component built-in circuit board, an inner-layer board containing components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet from the support side to the inner layer substrate. Examples of the member for heating and pressing the resin sheet to the inner layer substrate (hereinafter also referred to as "hot pressing member") include a heated metal plate (SUS hard plate) 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 resin sheet can sufficiently follow the surface unevenness of the inner layer substrate, not directly press the resin sheet.

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

The lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meiji Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Material Co., Ltd., and a batch type vacuum pressure laminator can be given.

After lamination, the laminated resin sheet may be subjected to smoothing treatment under atmospheric pressure (under atmospheric pressure), for example, by pressing a 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 continuously performed 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 conditions of the resin composition layer are not particularly limited, and conditions generally employed in 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 220 캜, 200 占 폚), and the curing time may be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 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 to a temperature of 50 占 폚 or more and less than 120 占 폚 (preferably 60 占 폚 or more and 115 占 폚 or less, more preferably 70 占 폚 or more and 110 占 폚 or less) It may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 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 may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. When the support is removed after the step (II), the removal of the support is carried out between the steps (II) and (III), between the steps (III) and (IV) Or the like. Further, if necessary, the multilayer wiring board may be formed by repeating the formation of the insulating layer and the conductor layer in the process (II) to the process (V). In this case, it is preferable that the thickness of the insulating layer (t1 in Fig. 1) between the respective conductor layers is within the above range.

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 in accordance with 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 well-known sequence and conditions commonly used in forming the insulating layer of the printed wiring board can be adopted. For example, swelling treatment with a swollen liquid, coarsening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer. The swelling liquid used for the harmonic treatment is not particularly limited, but examples thereof include an alkali solution and a surfactant solution, preferably an alkali solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Siculiganth P, Swelling Dip Sicurgis SBU manufactured by Atotech Japan Co., Ltd., and the like. The swelling treatment by the swelling liquid is not particularly limited, but can be carried out, for example, by immersing the swelling liquid at 30 캜 to 90 캜 for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling solution at 40 캜 to 80 캜 for 5 minutes to 15 minutes. The oxidizing agent used for the harmonic treatment is not particularly limited, and for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. 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 at 60 캜 to 80 캜 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 · Securigans P". An acidic aqueous solution is preferable as a neutralizing solution used for harmonization treatment, and commercially available products include, for example, "Reduction Solution · Securigans P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing liquid can be carried out by soaking the treated surface subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes. From the standpoint of workability and the like, it is preferable to immerse the object subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 to 70 캜 for 5 to 20 minutes.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. The square root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic average roughness (Ra) and the square root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughing machine.

Step (V) is a step of forming a conductor layer. Step (V) is a step of forming the first conductor layer when the conductor layer is not formed on the inner layer substrate, and when the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer, V) is a step of forming the second conductor 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 . The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy and copper- ). &Lt; / RTI &gt; Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer or nickel-chromium alloy, copper-nickel alloy, An alloy layer of copper-titanium alloy is preferable and an alloy layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer or nickel-chromium alloy is more preferable, Do.

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 kinds of metals or alloys are stacked. When the conductor layer is a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a pull additive method to form a conductor layer having a desired wiring pattern. In view of simplicity of manufacture, It is preferably formed by the additive method. Hereinafter, an example of forming the conductor layer by the semi-additive 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, and a conductor layer having a desired wiring pattern can be formed.

The resin sheet of the present invention can be suitably used even in the case where the printed wiring board is a component built-in circuit board, because it leads to a good insulating layer in terms of part embedding property. The component built-in circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may be an embodiment in which the insulating layer which is a cured product of the resin composition layer of the resin sheet and the buried wiring layer buried in the insulating layer.

[Semiconductor device]

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

Examples of the semiconductor device include various semiconductor devices provided in an electric product (such as a computer, a mobile phone, a digital camera and a television) and a vehicle (such as a motorcycle, a car, a train, have.

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) in a conductive portion of a printed wiring board. The &quot; conduction site &quot; is a &quot; location where electrical signals are transmitted from the printed wiring board &quot;, and the location may be either 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 of mounting the semiconductor chip at the time of manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the semiconductor chip is manufactured by 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 non-conductive film (NCF), and the like. Here, the "mounting method using the bumpless buildup layer (BBUL)" is a "mounting method in which the semiconductor chip is directly embedded in the concave portion of the printed wiring board to connect the wiring on the semiconductor chip and 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. In the following description, &quot; part (s) &quot; and &quot;% &quot;, representing amounts, means &quot; part by mass &quot; and &quot;% by mass &quot;

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

&Lt; Measurement of Peel Strength, 10-point Average Roughness (Rz Value) >

(Preparation of sample for measurement of peel strength, 10-point average roughness (Rz value)) [

(1) Underlayer treatment of inner layer circuit board

(A copper foil having a thickness of 18 mu m and a thickness of 0.8 mm, &quot; R1766 &quot; manufactured by Panasonic Corporation) having an inner layer circuit formed thereon was prepared as an inner layer circuit board, Manufactured by &quot; CZ8101 &quot;) to conduct copper surface roughening treatment (copper etching amount: 1.0 탆).

(2) Lamination of resin sheet

A resin sheet having a thickness of 10 占 퐉 of the resin composition layer prepared in Examples and Comparative Examples was applied to the inner layer by using a vacuum type vacuum laminator (Niko Material, Inc., two stage built-up laminator, CVP700) Both sides of the inner-layer circuit board were laminated to bond with the circuit board. 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. Then, hot pressing was performed at 100 占 폚 and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of resin composition

After laminating a resin sheet having a thickness of 10 占 퐉 of the resin composition layer, the resin composition layer was thermally cured at 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 substrate on which the insulating layer was exposed was immersed in a swelling liquid ("Swelling Deep Sucrygan G P" manufactured by Atotech Japan Co., Ltd., sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether) at 60 ° C for 10 minutes, (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%) for 20 minutes at 80 ° C, &Quot; Reduction Solution · Securigans P &quot;, aqueous solution of hydroxylamine sulfate) at 40 ° C for 5 minutes. Thereafter, it was dried at 80 DEG C for 15 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-additive method. That is, a plating process (a copper plating process using a chemical solution manufactured by Atotech Japan) including the processes of the following 1 to 6 was carried out to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of insulating layer surface with via hole)

The surface of the evaluation substrate a was cleaned using a Cleaning cleaner Securiganth 902 (trade name) at 60 캜 for 5 minutes.

2. Soft etching (cleaning in via hole)

The surface of the evaluation substrate a was treated with an aqueous sulfuric acid peroxodisulfate solution at 30 占 폚 for 1 minute.

3. Pre-dip (adjustment of charge on the insulating layer surface for Pd application)

The surface of the evaluation substrate a was treated with Pre.Dip Neoganth B (trade name) at room temperature for 1 minute.

4. Assignment of activator (application of Pd to the surface of insulating layer)

The surface of the evaluation substrate a was treated with Activator Neoganth 834 (trade name) at 35 캜 for 5 minutes.

5. Reduction (reduction of Pd given to insulating layer)

The surface of the evaluation substrate a was treated with a mixture of Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. (Trade name) at 30 ° C for 5 minutes.

6. Electroless copper plating process (depositing Cu on the surface of the insulating layer (Pd surface))

The surface of the evaluation substrate a was treated with a mixture solution of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name) and Reducer Cu And treated for 30 minutes. The thickness of the electroless copper plated layer formed was 1 占 퐉.

Subsequently, annealing was performed by heating at 150 DEG C for 30 minutes, and then an etching resist was formed and patterned by etching. Thereafter, copper sulfate electroplating was performed using a chemical solution manufactured by Atotech Japan Co., Ltd. to form a conductor layer having a thickness of 25 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;.

(Measurement of ten-point average roughness (Rz)) [

The evaluation substrate a before the conductor layer was formed was measured with a non-contact surface roughness machine ("WYKO NT3300" manufactured by Vico Instruments Co., Ltd.) using a VSI contact mode and a 50x lens to set the measurement range to 121 μm × 92 μm The maximum height roughness (Rz) described in Japanese Industrial Standards (JIS B0601-2001) was obtained from the obtained numerical values.

(Measurement of Peel Strength of Plated Conductor Layer)

The measurement of the peel strength of the plated conductor layer was performed on the evaluation board b in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a cut 10 mm in width and 100 mm in length was inserted into the conductor layer of the evaluation board b, the one end was peeled off and picked up with a collecting tool, and 35 mm was peeled in the vertical direction at a rate of 50 mm / The load (kgf / cm) was measured to determine the peel strength (peel strength). A tensile tester (&quot; AC-50C-SL &quot; manufactured by TSE) was used for measurement.

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

(Preparation of cured product for evaluation)

A resin sheet having a thickness of 25 占 퐉 of the resin composition layer prepared in Examples and Comparative Examples was 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;.

(Measurement of Glass Transition Temperature and Linear Thermal Expansion Coefficient)

The cured product for evaluation c was cut into test pieces having a width of 5 mm and a length of 15 mm. The test piece was subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer ("Thermo Plus TMA8310" manufactured by Rigaku Corporation). Specifically, after the test piece was mounted 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 two measurements, the coefficient of linear thermal expansion (ppm / 占 폚) in the plane direction in the range of glass transition temperature (占 폚) and 25 占 폚 to 150 占 폚 was calculated and the average value thereof was determined.

&Lt; Synthesis Example 1: Synthesis of polyimide resin 1 having polycyclic aromatic hydrocarbon skeleton >

A 500 mL separable flask equipped with a moisture quantifying machine connected to a reflux condenser, a nitrogen introducing tube, and a stirrer was prepared. To this flask was added 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of? -Butyrolactone, 20 g of toluene and 10 g of 5- (4-aminophenoxy) -3- [4- Yl) phenyl] -1,1,3-trimethylindane was added, and the mixture was stirred at 45 DEG C for 2 hours under a nitrogen stream to carry out the reaction to obtain a reaction solution.

Then, the reaction solution was heated, and the condensed water was azeotropically removed with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. It was confirmed that a predetermined amount of water was accumulated in the water quantitative handwriting machine and that the water spill was not observed. After confirming, the reaction solution was further heated and stirred at 200 占 폚 for 1 hour. Thereafter, the resultant was cooled to obtain a varnish containing 20 mass% of a polyimide resin having a 1,1,3-trimethylindane skeleton (hereinafter sometimes referred to as &quot; polyimide resin 1 &quot;). The obtained polyimide resin 1 had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The polyimide resin 1 had a weight average molecular weight of 12,000.

(X1)

(X2)

&Lt; Synthesis Example 2: Synthesis of polyimide resin 2 having polycyclic aromatic hydrocarbon skeleton >

29.6 g of the 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane was dissolved in 9,9-bis -Aminophenyl) fluorene was changed to 22.9 g. A varnish containing 20 mass% of a polyimide resin having fluorene skeleton (hereinafter sometimes referred to as &quot; polyimide resin 2 &quot;) was obtained in the same manner as in Synthesis Example 1 except for the above. The obtained polyimide resin 2 had a repeating unit represented by the following formula (X3) and a repeating unit represented by the above formula (X2). The weight average molecular weight of the polyimide resin 2 was 14,000.

(X3)

&Lt; Synthesis Example 3: Synthesis of polyimide resin 3 having no polycyclic aromatic hydrocarbon skeleton >

65.0 g of aromatic tetracarboxylic acid dianhydride ("BisDA-1000" manufactured by SABIC Japan), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were placed in a reaction vessel equipped with a stirrer, a thermometer, a thermometer and a nitrogen gas introducing tube And the solution was heated to 60 占 폚. Then, 43.7 g of dimer diamine ("PRIAMINE 1075" manufactured by Kuroda Japan Co., Ltd.) and 5.4 g of 1,3-bisaminomethylcyclohexane were added dropwise, followed by imidization reaction at 140 ° C. for 1 hour. Thus, a varnish (nonvolatile matter content of 30 mass%) containing dimer diamine polyimide resin was obtained (hereinafter sometimes referred to as &quot; polyimide resin 3 &quot;). The weight average molecular weight of the polyimide resin 3 was 25,000.

&Lt; Example 1 >

, 30 parts of a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent weight 180) and 30 parts of a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 269) Hexane and 15 parts of hexane was heated and dissolved while stirring, and then cooled to room temperature. In this mixed solution, an aminosilane-based coupling agent (manufactured by Shin-Etsu Kagaku Kogyo Preparation "KBM573") surface-treated spherical silica (mean particle diameter 0.078㎛, a specific surface area of 30.7m ² / g, Den kika Kagaku Kogyo Preparation "UFP 14 parts of phenol-based curing agent ("LA-3018-50P" manufactured by DIC Co., Ltd., hydroxyl group equivalent of about 151, 50% of solid content 50% of 2-methoxypropanol solution containing triazine skeleton), 100 parts of active ester curing agent 40 parts of a toluene solution of a nonvolatile component of about 223, an active group equivalent of about 223, and 40 parts of a varnish containing a polyimide resin 1 synthesized in Synthesis Example 1 (having a solid content of 20% by mass of? , 6 parts of a curing accelerator (&quot; DMAP &quot;, 4-dimethylaminopyridine, 5% by mass of solid content of methyl ethyl ketone (hereinafter abbreviated as &quot; MEK &quot;) solution) And uniformly dispersed to prepare resin varnish 1.

Two PET films with an alkyd resin-based release layer (&quot; AL5 &quot;, manufactured by LINTEX, thickness 38 mu m) were prepared as supports. The resin varnish 1 was uniformly coated on the release layer of each support so that the resin composition layer after drying had a thickness of 10 탆 and 25 탆 and dried at 70 to 95 캜 for 2 minutes to prepare a resin sheet 1.

&Lt; Example 2 >

In Example 1, 30 parts of a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 269) was mixed with 30 parts of a naphthol type epoxy resin ("ESN475V" manufactured by Shinetsettsu Sumikin Chemical Co., Change. Resin varnish 2 and resin sheet 2 were produced in the same manner as in Example 1 except for the above.

&Lt; Example 3 >

In Example 1, 30 parts of a biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 269) was changed to 30 parts of a biquilene type epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent weight: about 185) Respectively. Resin varnish 3 and resin sheet 3 were produced in the same manner as in Example 1 except for the above.

<Example 4>

20 parts of a varnish (solid content 20% by mass of? -Butyrolactone solution) containing polyimide resin 1 synthesized in Synthesis Example 1 was changed to 10 parts, and a phenoxy resin (manufactured by Mitsubishi Kagaku Co., Ltd.) 7 parts of &quot; YX6954BH30 &quot;, a 1: 1 solution of MEK and cyclohexanone in a solid content of 30 mass%) was added. Resin varnish 4 and resin sheet 4 were produced in the same manner as in Example 1 except for the above.

&Lt; Example 5 >

20 parts of a varnish (solid content 20% by mass of? -Butyrolactone solution) containing polyimide resin 1 synthesized in Synthesis Example 1 was added to 20 parts of a varnish containing polyimide resin 2 synthesized in Synthesis Example 2 (20 parts by mass of a? -Butyrolactone solution having a solid content of 20% by mass). Resin varnish 5 and resin sheet 5 were produced in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 1 &

20 parts of a varnish (solid content 20% by mass of? -Butyrolactone solution) containing the polyimide resin synthesized in Synthesis Example 1 was mixed with 20 parts of phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Kagaku Co., Ltd., % Of MEK and 1: 1 solution of cyclohexanone). Resin varnish 6 and resin sheet 6 were produced in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 2 &

20 parts of a varnish (solid content 20% by mass of? -Butyrolactone solution) containing polyimide resin synthesized in Synthesis Example 1 was added to 20 parts of a varnish containing polyimide resin 3 synthesized in Synthesis Example 3 A mixed solution of cyclohexanone and methylcyclohexane having a solid content of 30 mass%) was changed to 13 parts. Resin varnish 7 and resin sheet 7 were produced in the same manner as in Example 1 except for the above.

The components used in the preparation of Resin Compositions 1 to 7 and their blending amounts (in terms of nonvolatile components) are shown in the following table. The content (% by mass) of the component (D) in the following table indicates the content of the component (D) when the nonvolatile component in the resin composition is 100% by mass.

In Examples 1 to 5, even when the components (E) to (G) were not contained, it was confirmed that the results were the same as those of the above-mentioned Examples although there were differences in the degree.

1: first conductor layer
11: Main surface of first conductor layer
2: second conductor layer
21: Main surface of second conductor layer
3: Insulating layer
t1: the distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers)
t2: thickness of the entire insulating layer

Claims (18)

(A) an epoxy resin,
(B) an active ester-based curing agent,
(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and
(D) an inorganic filler,
(D) has an average particle diameter of 100 nm or less. (A) an epoxy resin,
(B) an active ester-based curing agent,
(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and
(D) an inorganic filler,
(D) has a specific surface area of 15 m ² / g or more. The resin composition according to claim 1 or 2, wherein the polycyclic aromatic hydrocarbon skeleton is an aromatic hydrocarbon skeleton in which an aromatic ring is condensed with a 5-membered ring compound. The resin composition according to claim 1 or 2, wherein the polycyclic aromatic hydrocarbon skeleton is at least one of an indane skeleton and a fluorene skeleton. 3. The resin composition according to claim 1 or 2, wherein the component (C) has a weight average molecular weight of 5,000 or more. The resin composition according to claim 1 or 2, wherein the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure. 7. The method for producing a polyolefin film according to claim 6, wherein the mass ratio of the recurring unit having a polycyclic aromatic hydrocarbon skeleton to the recurring unit having an imide structure (mass of recurring unit having polycyclic aromatic hydrocarbon skeleton / mass of recurring unit having imide structure) Lt; 2 &gt; or less. The resin composition according to any one of claims 1 to 3, wherein the content of the component (C) is 0.1% by mass or more and 3% by mass or less when the content of the nonvolatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 5, wherein the content of the component (B) is 1% by mass or more and 25% by mass or less when the content of the nonvolatile component in the resin composition is 100% by mass. The resin composition according to Claim 1 or 2, wherein the content of the component (D) is 30% by mass or more and 80% by mass or less when the content of the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, further comprising (E) a curing agent. 12. The resin composition according to claim 11, wherein the (E) curing agent is a phenolic curing agent. 13. The resin composition according to any one of claims 1 to 12, which is used for forming an insulating layer for forming a conductor layer. The resin composition according to claim 1 or 2, which is for forming an insulating layer of a printed wiring board. The resin composition according to claim 1 or 2, which is used for forming an interlayer insulating layer of a printed wiring board. 15. A resin sheet comprising a support and a resin composition layer according to any one of claims 1 to 15 provided on the support. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
Wherein the insulating layer is 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.

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