KR20180123977A - Resin composition - Google Patents

Abstract

An objective of the present invention is to provide a resin composition which has excellent thin film insulation properties even when an inorganic filler having a small average particle diameter or a large specific surface area is used; and allows users to obtain a balanced cured product capable of maintaining the adhesion with a conductive layer after environmental testing under a high temperature and high humidity environment. The resin composition includes (A) an epoxy resin, (B) a curing agent, (C) a polycarbonate resin, and (D) an inorganic filler, wherein the average particle diameter of (D) the inorganic filler is 100 nm or less; or includes (A) an epoxy resin, (B) a curing agent, (C) a polycarbonate resin, and (D) an inorganic filler, wherein the specific surface area of (D) the inorganic filler is 15 m^2/g or more.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device which can be obtained by using the resin composition.

As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated is known. In the build-up method, generally, the insulating layer is formed by curing the resin composition. For example, Patent Document 1 discloses an epoxy resin composition comprising an epoxy resin, an active ester compound, a carbodiimide compound, a thermoplastic resin and an inorganic filler, wherein when the content of the inorganic filler is 100 mass% By mass or more and 40% by mass or more.

Japanese Unexamined Patent Application Publication No. 2016-27097

In general, it has been known that when a large amount of inorganic filler is used, it is difficult to control the lamination property due to lowering of the filling property of the film due to an increase in melt viscosity. The present inventors have found that when the average particle diameter is small It has been found that when an inorganic filler having a large surface area is contained, it becomes difficult to maintain the adhesion between the conductor layer such as copper foil and the insulating layer after the environmental test under a high temperature and high humidity environment. In order to respond to future demands for fine wiring, it is required to maintain adhesion after environmental testing even when an inorganic filler having a small average particle diameter or a large specific surface area is used.

It is an object of the present invention to provide a resin composition which is excellent in thin film insulation property even when an inorganic filler having a small average particle diameter or a large specific surface area is used and can maintain adhesiveness with a conductor layer after an environmental test under a high temperature and high humidity environment, A resin composition capable of obtaining a balanced cured product; A resin sheet containing 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 even when an inorganic filler having a small average particle diameter or a large specific surface area is used, the polycarbonate resin is contained in the resin composition, And the adhesion between the insulating layers can be maintained, thereby completing the present invention.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a polycarbonate resin, and (D)

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

[2] A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a polycarbonate resin, and (D)

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

[3] The resin composition according to [1] or [2], wherein the content of the component (D) is 50% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

[4] The resin composition according to any one of [1] to [4], wherein the component (B) is at least one selected from the group consisting of a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent and a carbodiimide curing agent. 3]. ≪ / RTI >

[5] The resin composition according to any one of [1] to [4], wherein the component (B) comprises an active ester type curing agent.

[6] The resin composition according to any one of [1] to [5], wherein the component (C) is at least one of an aliphatic skeleton-containing polycarbonate resin and an aromatic skeleton-containing polycarbonate resin.

[7] The resin composition according to any one of [1] to [6], wherein the component (C) has a number average molecular weight of 1,000 to 200,000.

[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 30% by mass or less when the resin component is 100% by mass.

[9] A resin composition according to any one of [1] to [8], which is used for forming an insulating layer for forming a conductor layer.

[10] The resin composition according to any one of [1] to [9], which is used for forming an insulating layer of a printed wiring board.

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

[12] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [11] provided on the support.

[13] A resin sheet according to [12], wherein the resin composition layer has a thickness of 15 μm or less.

[14] 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 interval between the first conductor layer and the second conductor layer is 6 [ [12] The resin sheet according to [12] or [13], wherein the resin sheet is for forming the insulating layer.

[15] 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,

The insulating layer is a cured product of the resin composition according to any one of [1] to [11].

[16] The printed wiring board according to [15], wherein the interval between the first conductor layer and the second conductor layer is 6 μm or less.

[17] A semiconductor device comprising the printed wiring board according to [15] or [16].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition which is excellent in thin-film insulation even when an inorganic filler having a small average particle diameter or a large specific surface area is used and in which the adhesion between the conductor layer and the conductor layer can be maintained after environmental testing under a high- A resin composition capable of obtaining a cured product; A resin sheet containing 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]

The resin composition of the first embodiment of the present invention is a resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a polycarbonate resin, and (D) an inorganic filler, wherein (D) The particle diameter is 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) a curing agent, (C) a polycarbonate resin, and (D) Is not less than 15 m < 2 > / g. The resin compositions of the first and second embodiments are excellent in the thin film insulation property even when an inorganic filler having a small average particle diameter or a large specific surface area is contained in the polycarbonate resin (C) It is possible to obtain a cured product which can maintain the adhesion between the conductive layer and the conductive layer even after the environmental test. In general, a cured product capable of maintaining high adhesiveness even after an environmental test under such a high-temperature and high-humidity environment can exhibit high adhesiveness over a long period of time.

The resin composition may contain, in addition to the components (A) to (D), a curing accelerator (E), a flame retardant (F), and optional additives (G), if necessary. 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 biquilene 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, heterocyclic epoxy resin, spiro-ring-containing epoxy resin, cyclohexane type epoxy resin, epoxy resin having a butadiene structure, Epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin , Tree and the like can be mentioned methyl olhyeong epoxy resin, tetraphenyl ethane epoxy resin. 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 defined as 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 a liquid epoxy resin (hereinafter referred to as " liquid epoxy resin ") and a solid epoxy resin (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, and a bisphenol A- desirable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "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 Sumikin Kagaku Co., and EX-721 (a glycidyl ester type epoxy resin (Cycloaliphatic epoxy resin having an ester skeleton), " PB-3600 " (epoxy resin having a butadiene structure), " ZX1658 ", " ZX1658GS (Liquid 1,4-glycidyl cyclohexane type epoxy 630LSD " (glycidylamine type epoxy resin) manufactured by Mitsubishi Kagaku Co., 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 type epoxy resins, phenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins and tetraphenyl ethane type epoxy resins are preferable. Bisphenol AF type epoxy resins and biphenyl type epoxy The resin is more preferable. 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 " (biphenyl type epoxy resin), " NC7000L " ESN475V "(naphthalene type epoxy resin)," ESN485 "(naphthol novolak type epoxy resin)," YX4000H "," YX4000 ", and" YL6121 "(manufactured by Mitsubishi Kagaku Co., PG-100 "," CG-500 "manufactured by Osaka Gas Chemical Co., Ltd.," YL7760 "manufactured by Mitsubishi Kagaku Co., Ltd.)," YX4000HK "(biquileneol type epoxy resin) Quot; jER1010 " (solid bisphenol A type epoxy resin) and " jER1031S " (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Kagaku Co., . 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 together as the component (A), their ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 1 to 1:20 in terms of the mass ratio. When the ratio of the liquid epoxy resin and the solid epoxy resin is in this range, sufficient adhesiveness is formed when i) the resin is used in the form of a resin sheet, ii) sufficient flexibility is obtained when the resin 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 the above i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 1 to 1: 5, : 1 to 1: 3 is more preferable.

The content of the component (A) in the resin composition is preferably 10% by mass or more, more preferably 10% 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 20% 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 it is preferably 40 mass% or less, more preferably 35 mass% or less, further preferably 30 mass% or less.

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

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. With this range, the crosslinked density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of the resin containing one equivalent of epoxy group.

The weight average molecular weight of the 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 a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(B) Hardener>

The resin composition contains (B) a curing agent. The component (B) 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, an active ester series curing agent, a benzoxazine series curing agent, a cyanate ester series curing agent, And carbodiimide-based curing agents. Among them, from the viewpoint of improving the insulation reliability, the component (B) is preferably selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent and a carbodiimide- More preferably at least one species selected from the group consisting of an active ester-based curing agent, a phenol-based curing agent, and a naphthol-based curing agent, and more preferably an active ester-based curing agent. 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", "MEH-7851" manufactured by Meiwa Chemical Industries, Ltd., "NHN" SN375 "," SN-495V "," SN375 "," SN395 "," SN375 "," TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "and" EXB-9500 "manufactured by DIC Corporation.

The active ester-based curing agent is not particularly limited, but generally, an ester group having high reactivity such as esters of phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds is used in an amount of 2 Are preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Specifically, there can be mentioned an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, a benzoyl compound of phenol novolac Active ester compounds are preferable, and active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" refers to a divalent structural unit comprising phenylene-dicyclopentylene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000H-65TM ", and the like are available as commercial products of the active ester- EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure, an acetal compound of phenol novolac as an active ester compound containing a naphthalene structure," EXB-8000L-65TM "," EXB-8150-65T " "YLH1026" (manufactured by Mitsubishi Kagaku) as an active ester compound containing benzoylate of phenol novolac, "DC808" (manufactured by Mitsubishi Kagaku Co., Ltd.) as an active ester compound, , YLH1026 (manufactured by Mitsubishi Kagaku Co., Ltd.), YLH1030 (manufactured by Mitsubishi Kagaku Co., Ltd.), and YLH1048 (manufactured by Mitsubishi Kagaku Co., Ltd.) as the active ester curing agent which is benzoylate of phenol novolac Kusadasi car manufacturer Mitsubishi) and the like.

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 phenol novolacs and cresol novolacs such as bis (4-cyanophenyl) thioether and bis (4-cyanatephenyl) ether, and polyfunctional cyanate resins derived from these cyanate resins And a prepolymer. 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.,

The proportion of the epoxy resin and the curing agent is preferably in the range of 1: 0.01 to 1: 2, more preferably 1: 0.05 to 1: 3, in the ratio of [the total number of epoxy groups of epoxy resin]: [the total number of reactors of the curing agent] , More preferably from 1: 0.1 to 1: 1.5. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, and the like, depending on the kind of the curing agent. The total number of epoxy groups in the epoxy resin refers to a value obtained by dividing the solid component weight of each epoxy resin by the epoxy equivalent for all epoxy resins and the total number of reactors in the curing agent means that the solid mass of each curing agent is equivalent to the reactor Divided by the total amount of the curing agent. By setting the ratio of the epoxy resin and the curing agent to this range, the heat resistance of the cured product of the resin composition layer is further improved.

The content of the component (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition. The upper limit is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 21 mass% or less. By making the content of the component (B) fall within this range, the adhesion with the conductor layer can be improved.

&Lt; (C) Polycarbonate resin >

The resin composition contains (C) a polycarbonate resin. In the present invention, by containing the polycarbonate resin (C) in the resin composition, the adhesion between the conductor layer and the insulating layer after the environmental test under a high-temperature and high-humidity environment can be improved 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 that can be maintained. The polycarbonate resin (C) exhibits high hydrophobicity as compared with thermoplastic resins such as an amide resin and a phenoxy resin, so that the polycarbonate resin (C) hardly causes hydrolysis. As a result, it can be considered that the insulating layer is not deteriorated even after the environmental test under a high-temperature and high-humidity environment, and the adhesion with the conductor layer is maintained. The polycarbonate resin (C) is considered to cause intermolecular interaction between the component (A), the component (B) and the component (D), and as a result, the adhesion force between the components in the high temperature and high humidity environment . In particular, it can be considered that the above-mentioned interaction largely acts at the interface between the inorganic filler (D) and the resin component such as the component (A) or the component (C). (D) The inorganic filler has a small average particle diameter or a large specific surface area, and therefore the interface is wide. Therefore, it can be considered that the reason why the bonding force at the interface can be maintained at a high level by the above-described interaction is that the insulating layer does not deteriorate even after the environmental test under a high temperature and high humidity environment and the adhesive force with the conductor layer is maintained have.

The component (C) is not particularly limited as long as it has a carbonate group, and examples thereof include an aliphatic skeleton-containing polycarbonate resin, an aromatic skeleton-containing polycarbonate resin, an aromatic skeleton and a polycarbonate resin containing an aliphatic skeleton. The component (C) may be used alone or in combination of two or more. Here, the carbonate group means a group represented by &quot; -O-C (= O) - &quot;.

The component (C) can be generally produced by reacting a polyhydroxy compound with a carbonate group precursor, and has a structural unit derived from a polyhydroxy compound. The polyhydroxy compound and the carbonate group precursor may be used singly or in combination of two or more. The component (C) may also be produced by reacting a copolymer obtained by copolymerizing two or more polyhydroxy compounds with a carbonate group precursor. A structural unit means a structure in which one or two hydrogen atoms are removed from a compound.

Examples of the carbonate group precursor include carbonic ester, phosgene, and the like.

Examples of the polyhydroxy compound include an aliphatic skeleton-containing polyhydroxy compound and an aromatic skeleton-containing polyhydroxy compound. Here, the aliphatic skeleton-containing polyhydroxy compound refers to a polyhydroxy compound containing no aromatic ring in the molecule, and the aromatic skeleton-containing polyhydroxy compound refers to a polyhydroxy compound containing an aromatic ring in the molecule. The polycarbonate resin obtained by using the aliphatic skeleton-containing polyhydroxy compound and the polycarbonate resin obtained by using the aliphatic skeleton-containing polycarbonate resin and the aromatic skeleton-containing polyhydroxy compound are mixed with the aromatic skeleton-containing polycarbonate resin and the aliphatic skeleton- A polycarbonate resin obtained by using a dihydroxy compound and an aromatic skeleton-containing dihydroxy compound is referred to as a polycarbonate resin containing an aromatic skeleton and an aliphatic skeleton.

From the viewpoint of obtaining a cured product having excellent adhesion after environmental testing under a high temperature and high humidity environment even when an inorganic filler having a small average particle diameter or a large specific surface area is used as the aromatic skeleton-containing polyhydroxy compound, the aromatic skeleton- . Examples of the aromatic skeleton-containing dihydroxy compound include bisphenol and naphthalene diol. Even when an inorganic filler having a small average particle diameter or a large specific surface area is used, the aromatic skeleton-containing dihydroxy compound is excellent in adhesion after environmental testing under a high- From the standpoint of obtaining a cured product, bisphenol is preferable. That is, the aromatic skeleton-containing polycarbonate resin is preferably a carbonate resin having a bisphenol structural unit. Here, bisphenol is a generic term for compounds having two hydroxyphenyl groups.

Examples of the bisphenol constituting the bisphenol structural unit include bisphenol A, bisphenol B, bisphenol C, bisphenol E, bisphenol F, and bisphenol Z, with bisphenol A and bisphenol C being preferred.

As the aromatic skeleton-containing polycarbonate resin, commercially available products can be used. Examples of commercially available products include "FPC2136", "FPC0220", "PCZ200", and "FPC0330" manufactured by Mitsubishi Gas Kagaku Co.,

As the aliphatic skeleton-containing polyhydroxy compound, from the viewpoint of obtaining a cured product excellent in adhesion after environmental testing under a high temperature and high humidity environment even when an inorganic filler having a small average particle diameter or a large specific surface area is used, . Examples of the aliphatic skeleton-containing dihydroxy compound include diol compounds and the like. That is, the aliphatic skeleton-containing polycarbonate resin is preferably a carbonate resin having a diol structural unit. The diol compound constituting the diol structural unit includes, for example, 6-hexamethylene diol.

As the aliphatic skeleton-containing polycarbonate resin, commercially available products can be used. Commercially available products include, for example, "T5652", "G3452", and "G4672" manufactured by Asahi Kasei Corporation.

The component (C) is preferably at least one selected from the group consisting of an aliphatic skeleton-containing polycarbonate resin and an aromatic skeleton-containing polycarbonate resin, and any one of a carbonate resin having a diol structural unit and a polycarbonate resin having a bisphenol structural unit Or more.

The number average molecular weight of the component (C) is preferably 1000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more, from the viewpoint of lowering the melt viscosity of the resin composition. Further, from the viewpoint of obtaining a cured product having excellent adhesion after environmental testing under a high temperature and high humidity environment, it is preferably 200,000 or less, more preferably 100,000 or less, further preferably 50,000 or less, or 30,000 or less. The number average molecular weight can be measured according to the description of &quot; Measurement of Number Average Molecular Weight of Polycarbonate Resin &quot;

The content of the component (C) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on 100% by mass of the resin component. The upper limit is preferably 30 mass% or less, more preferably 20 mass% or less, further preferably 10 mass% or less. When the content of the component (C) is within this range, adhesion after environmental testing under a high temperature and high humidity environment can be improved even when an inorganic filler having a small average particle diameter or a large specific surface area is used. Here, the "resin component" refers to a component other than the inorganic filler (D) to be described later, which is a nonvolatile component constituting the resin composition.

<(D) Inorganic filler>

The resin composition of the first embodiment contains (D) an inorganic filler, and (D) the inorganic filler has an average particle diameter of 100 nm or less. The resin composition of the second embodiment contains (D) an inorganic filler, and (D) the inorganic filler has a specific surface area of 15 m 2 / g or more.

The material of the inorganic filler is not particularly limited as long as it is an inorganic compound. Examples of the filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Magnesium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, Titanium, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. As the silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like can be given. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

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 thin film insulation. 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, and further preferably 80 nm or less, from the viewpoint of thin film insulation. 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 diameter distribution of the inorganic filler can be measured with a laser diffraction scattering type particle diameter distribution measuring apparatus, and the median diameter can be measured with an average particle diameter. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle diameter distribution measuring device, "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 15 m2 / g or more, more preferably 20 m2 / g or more, and further preferably 30 m2 / g or more, from the viewpoint of thin film insulation. The upper limit value 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, from the viewpoint of improving the lamination property.

The specific surface area of the inorganic filler in the first embodiment is preferably at least 15 m 2 / g, more preferably at least 20 m 2 / g, even more preferably at least 30 m 2 / g, from the viewpoint of thin film insulation . 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 is 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 improving moisture resistance and dispersibility, the inorganic filler is preferably selected from the group consisting of 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, Compound, titanate-based coupling agent, and the like, and is more preferably treated with an aminosilane-based coupling agent. Examples of commercially available products of the surface treatment agent 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.

The degree of surface treatment by the surface treatment agent is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent per 100 parts by mass of the component (D) from the viewpoint of improving the dispersibility of the inorganic filler, 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. The amount of carbon per unit surface area of the inorganic filler is preferably at least 0.02 mg / m 2, more preferably at least 0.1 mg / m 2, and most preferably at least 0.2 mg / m 2 from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of suppressing the increase of the melt viscosity and the melt viscosity in the sheet form of the resin varnish, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less and still more preferably 0.5 mg / m 2 or less.

The 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 50% by mass or more, more preferably 51% by mass or more, still more preferably 50% by mass or more, more preferably 100% Is not less than 52% by mass. The upper limit is preferably 80 mass% or less, more preferably 70 mass% or less, further preferably 65 mass% or less.

When the content of the component (D) is d and the content of the component (C) is c when the content of the nonvolatile component in the resin composition is 100 mass% and the content of the component (D) is 100 mass% , and c / d is preferably 0.001 or more, more preferably 0.003 or more, further preferably 0.005 or more, preferably 1 or less, more preferably 0.5 or less, further preferably 0.1 or less. By making c / d fall within this range, adhesion after environmental testing under a high temperature and high humidity environment can be improved even when an inorganic filler having a small average particle diameter or a large specific surface area is used.

<(E) Curing accelerator>

In one embodiment, the resin composition may contain (E) 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 kinds.

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; amines such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) Diazabicyclo (5,4,0) undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- , 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, for example, &quot; P200-H50 &quot; manufactured by Mitsubishi Chemical Corporation.

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 is 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 (II) acetylacetonate 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, Is 0.08 mass% or more. The upper limit is preferably 3 mass% or less, more preferably 2 mass% or less, further preferably 1 mass% or less. By setting the content of the curing accelerator within this range, a cured product having excellent adhesion after environmental testing under a high temperature and high humidity environment can be obtained even when an inorganic filler having a small average particle diameter or a large specific surface area is used.

<(F) Flame Retardant>

In one embodiment, the resin composition may contain (F) a flame retardant. Examples of the flame retardant include a phosgene compound, an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicon-based flame retardant, a metal hydroxide, and the like. The flame retardant may be used alone, or two or more thereof may be used in combination.

The phosgene compound is not particularly limited as long as it is a cyclic compound containing nitrogen and phosphorus as constituent elements, but the phosgene compound is preferably a phosgene compound having a phenolic hydroxyl group.

Specific examples of the phosgene compound include "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Otsuka Chemical Co., FP-110 "," FP-300 ", and" FP-400 ", and" SPH-100 "manufactured by Otsuka Kagaku Co., Ltd. is preferable.

As the flame retardant other than the phosgene compound, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihatsu Kagakuko Co., As the flame retardant, it is preferable that hydrolysis is difficult, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

When the resin composition contains a flame retardant, the content of the flame retardant is preferably not less than 0.3% by mass, more preferably not less than 0.5% by mass, further preferably not less than 0.7% by mass, based on 100% by mass of the nonvolatile component in the resin composition to be. The upper limit is preferably 5 mass% or less, more preferably 4 mass% or less, further preferably 3 mass% or less.

&Lt; (G) Optional additives >

In one embodiment, the resin composition may further contain optional additives, if necessary. Examples of such optional additives include thermoplastic resins, organic fillers, organic copper compounds, organic zinc compounds, and organic cobalt An organic metal compound such as a compound, and a resin additive such as a thickener, a defoaming agent, a leveling agent, an adhesion-imparting agent, and a coloring agent.

Examples of the thermoplastic resin include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, Ether resins, polyether ether ketone resins, and polyester resins. However, the thermoplastic resin referred to herein does not include the (C) polycarbonate resin.

As the thermoplastic resin, a commercially available product may be used. For example, "YX7553BH30", "YX7891BH30" manufactured by Mitsubishi Kagaku Co., Ltd., KS series manufactured by Sekisui Chemical Co., Ltd., "Rika coat SN20" "Rika coat PN20", "OPE-2St 1200" manufactured by Mitsubishi Gas Kagaku Co., Ltd., and the like.

As the organic filler, any organic filler which can be used for forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, silicon particles and the like. As the rubber particles, commercially available products may be used, for example, "EXL2655" manufactured by Dow Chemical Co., Ltd., "AC3401N" manufactured by Aikoko Co., Ltd., and "AC3816N".

&Lt; Physical properties and uses of resin composition >

The cured product obtained by thermosetting the resin composition at 100 占 폚 for 30 minutes and then at 180 占 폚 for 20 minutes exhibits excellent insulation resistance even in the case of thin film insulation, that is, even when the cured product is a thin film. Specifically, when the resin composition is thermally cured at 100 占 폚 for 30 minutes and further at 180 占 폚 for 30 minutes, when the surface of the cured product is subjected to the roughening treatment test, even if the cured product is thin, It represents the resistance value. The insulation resistance value of a cured product having a thickness of 5 ± 0.5 μm is preferably not less than 0.1 × 10 ⁸ Ω, more preferably not less than 0.5 × 10 ⁸ Ω, and still more preferably not less than 1 × 10 ⁸ Ω. The upper limit is not particularly limited, but may be 100 x 10 < ¹² > The measurement of the insulation resistance value can be performed according to the method described in &quot; Evaluation of insulation reliability of insulation layer &quot;

The cured product obtained by thermally curing the resin composition at 190 占 폚 for 90 minutes exhibits excellent copper peel strength (adhesion) before environmental testing. That is, the insulating layer having excellent adhesion before the environmental test is formed. The copper foil peel strength before environmental testing is preferably at least 0.45 kgf / cm, more preferably at least 0.50 kgf / cm, and even more preferably at least 0.55 kgf / cm. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The copper foil peel strength before the environmental test can be measured according to the description of &quot; Measurement of copper foil peel strength (adhesion 1) &quot;

The cured product obtained by thermosetting the resin composition at 190 占 폚 for 90 minutes shows a characteristic that the copper foil peel strength (adhesion) after the environmental test is excellent. That is, an insulating layer which is excellent in adhesion after an environmental test and can exhibit high adhesiveness over a long period of time is formed. The copper foil peel strength after the environmental test is preferably at least 0.20 kgf / cm, more preferably at least 0.21 kgf / cm, even more preferably at least 0.25 kgf / cm. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The copper foil peel strength before the environmental test can be measured according to the description of &quot; Measurement of copper foil peel strength (adhesion 2) after internal environmental test (HAST) &quot;

The resin composition of the present invention is excellent in thin film insulation and can form an insulating layer capable of maintaining adhesiveness with a conductor layer after an environmental test under a high temperature and high humidity environment. 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). Further, the resin composition of the present invention can be suitably used even when the printed wiring board is a component built-in circuit board, because an insulating layer with a good part filling property can be formed. The resin composition of the present invention is a resin composition for forming the insulating layer for forming a conductor layer (including a rewiring layer) on an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer) It can be suitably used.

[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 15 占 퐉 or less, more preferably 13 占 퐉 or less, still more preferably 10 占 퐉 or less from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation property , Or 8 탆 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, 1.5 占 퐉 or more, 2 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 sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN" (TAC), polyether sulfide (PES), polyether sulfone (PES), and the like, such as polyesters, polycarbonates ), 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 the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, May be used.

The support may be subjected to a mat 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. As the release agent used for the release layer of the release layer-adhered support, for example, one or more release agents selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin can be mentioned. SK-1, &quot; &quot; AL-5 &quot;, and &quot; AL-5 &quot;, manufactured by LINTEX Corporation, which is a PET film having a releasing layer mainly composed of an alkyd resin releasing agent as a main component, -7 &quot; manufactured by Toray Industries, Inc., &quot; Lumirror T60 &quot; manufactured by Toray Industries, Inc., Purex manufactured by Teijin, 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. As such other layers, for example, a protective film based on a support formed on a surface of the resin composition layer not bonded to a support (that is, a surface opposite to the support) may, for example, be mentioned. The thickness of the protective film is not particularly limited, but is, for example, 1 탆 to 40 탆. By laminating a protective film, adhesion and scratches of dust and the like to the surface of the resin composition layer can be suppressed.

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, And the like; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. 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 jetting. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. For example, 30 to 60 mass% of the organic solvent is used, the resin varnish is dried at 50 to 150 DEG C for 3 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.

The resin sheet of the present invention forms an insulating layer (cured product of the resin composition layer) capable of maintaining adhesion between the resin layer and the conductor layer even after the environmental test under a thin film insulation property and a high temperature and high humidity environment. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet (for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and can be suitably used as a resin sheet for forming an interlayer insulating layer of a printed wiring board Resin sheet for an interlayer insulating layer of a wiring board). Further, for example, in 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, (Preferably not more than 5.5 탆, more preferably not more than 5 탆) between the first and second conductor layers (the thickness of the insulating layer between the first and second conductor layers) Can be made excellent.

[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 formed 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).

Since the insulating layer is formed by the cured product of the resin composition of the present invention, it has excellent thin film insulation. Therefore, 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 further 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) means the distance between the major surface 11 of the first conductor layer 1 and the distance Refers to the thickness t1 of the insulating layer 3 between the main surfaces 21 of the two conductor layers 2. The first and second conductor layers are conductor layers which are adjacent to each other with an insulating layer interposed therebetween, and the main surface 11 and the main surface 21 face each other.

The total thickness t2 of the insulating layer is preferably 15 占 퐉 or less, more preferably 13 占 퐉 or less, and further preferably 10 占 퐉 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 comprising the following steps (I) and (II) using the resin sheet described above.

(I) Step of laminating a resin composition layer of a resin sheet on an inner layer substrate so as to be bonded to an inner layer substrate

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

The term &quot; inner layer substrate &quot; used in the step (I) means a member to be 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 side or both sides 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 in which an insulating layer and / or a conductor layer is to be further formed 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 to the inner layer substrate on the support side. Examples of the member for heating and pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as "hot pressed member") include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). It is also preferable to press the heat-press member through an elastic material such as heat-resistant rubber such that the heat-press member is not pressed directly onto the resin sheet but the resin sheet sufficiently follows the surface unevenness of the inner layer substrate.

The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum laminating method, the heat-pressing temperature is preferably in the range of 60 占 폚 to 160 占 폚, more preferably 80 占 폚 to 140 占 폚, the heat pressing pressure is preferably 0.098 MPa to 1.77 MPa, Is in the range of 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably in the range of 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. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meikishesakusho Co., Ltd., a plastic applicator manufactured by Nikko Materials Company, and a batch type vacuum pressure laminator.

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

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

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

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

For example, the thermosetting condition of the resin composition layer varies depending on the kind of the resin composition and the like, but the curing temperature is preferably 120 deg. C to 240 deg. C, more preferably 150 deg. C to 220 deg. C, To 200 캜. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 90 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before thermosetting the resin composition layer. For example, before the resin composition layer is thermally cured, the resin composition layer is heated at a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 115 ° C or less, more preferably 70 ° C or more and 110 ° C or less) It may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes).

In the production of the printed wiring board, the step of (III) piercing the insulating layer, (IV) the step of roughening the insulating layer, and the step of forming the conductor layer (V) 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 step (II) and the step (III), between the step (III) and the step (IV) ). Further, the multilayer wiring board may be formed by repeatedly forming the insulating layer and the conductor layer in the process (II) to the process (V), if necessary. 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.

The 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 procedure and condition of the roughening treatment are not particularly limited, and a known procedure and condition commonly used in forming the insulating layer of the printed wiring board can be adopted. For example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are 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, the swelling liquid is an alkali solution. More preferably, the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Deep Sucrygan G P" and "Swelling Deep Sucralgan SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment by the swelling liquid is not particularly limited, but can be performed, 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 in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40 占 폚 to 80 占 폚 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 may 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 to 60 占 폚 to 80 占 폚 for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, for example, alkaline permanganic acid solutions such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd. and "Dozing Solution Securigans P" may be mentioned. An acidic aqueous solution is preferable as the neutralization solution used in the harmonization treatment, and commercially available products include, for example, &quot; Reduction Solution Securigant P &quot; manufactured by Atotech Japan Co., The treatment with the neutralizing liquid can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes. 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 mean roughness (Ra) and square-root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer. Step (V) is a step of forming a first conductor layer in the case where a conductor layer is not formed on the innerlayer substrate, and when the conductor layer is formed on the innerlayer 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 do. 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, Alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or a nickel-chromium alloy, a copper-nickel alloy And an alloy layer of a copper-titanium alloy is preferable and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or an alloy layer of a nickel- chromium alloy is more preferable, Is more preferable.

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

The thickness of the conductor layer is generally 3 mu m to 35 mu m, preferably 5 mu m to 30 mu m, though it depends on the design of the desired printed wiring board.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of an insulating layer by a conventionally known technique such as a semi-custom method or a pull-on-fill method. In view of simplicity of manufacture, It is preferable to form it by a customary method. Hereinafter, an example in which the conductor layer is formed by the semi-

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.

Since the resin sheet of the present invention forms an insulating layer with good part embedding property, the resin sheet can be suitably used even when the printed wiring board is a component built-in circuit board. 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 provided with an insulating layer which is a cured product of the resin composition layer of the resin sheet and a buried wiring layer embedded 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 (e.g., a computer, a mobile phone, a digital camera and a television) and a vehicle (e.g., a motorcycle, an automobile, a tank, .

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) to a conductive portion of a printed wiring board. The "conduction point" is a "point for transmitting electrical signals on the printed wiring board", and may be a surface or a buried point. 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 can function effectively. Specifically, the method can be applied to a wire bonding mounting method, a flip chip mounting method, a bumpless buildup layer (BBUL) 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)" refers to a "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board".

Example

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these examples. In the following description, &quot; parts &quot; and &quot;% &quot; representing quantities mean &quot; part by mass &quot; and &quot;% by mass &quot;, respectively, unless otherwise specified.

&Lt; Example 1: Production of Resin Composition 1 >

, 10 parts of a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 180), 15 parts of a biphenyl type epoxy resin ("YX4000H" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent weight: about 190) , 10 parts of an epoxy resin ("YL7760" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent of about 238), 3 parts of a phosgene resin (SPH-100 manufactured by OTSUKA KAGAKUSA CORPORATION), 10 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Kagaku Co., 20895) were dissolved by heating in 50 parts of MEK while stirring.

After cooling to room temperature, 20 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, a toluene solution of a solid content of 65% by mass), 20 parts of a phenolic curing agent , 25 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), 5 parts by mass of a solid content of MEK solution), 3 parts of a spherical silica 75 parts of UFP-30 manufactured by Kagaku Kogyo Co., Ltd., average particle diameter 0.078 mu m, specific surface area 30.7 m2 / g) were mixed and uniformly dispersed by a high-speed rotary mixer, Followed by filtration to obtain a resin composition 1.

&Lt; Example 2: Production of Resin Composition 2 >

In Example 1, 3 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Kagaku Co., Ltd.) was changed to 3 parts of polycarbonate resin ("FPC0220" manufactured by Mitsubishi Gas Chemical Company, number average molecular weight 18911). Resin composition 2 was produced in the same manner as in Example 1 except for the above.

&Lt; Example 3: Production of resin composition 3 >

In Example 1, 3 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Company) was changed to 3 parts of a polycarbonate resin ("T5652" manufactured by Asahi Kasei Corporation, number average molecular weight: 2035). Resin composition 3 was produced in the same manner as in Example 1 except for the above.

&Lt; Example 4: Production of Resin Composition 4 >

20 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent: about 223, solid component: 65% by mass toluene solution) in Example 1 was mixed with an active ester type curing agent (EXB9416-70BK (MIBK (methyl isobutyl ketone) solution having an active group equivalent of about 274 and a solid content of 70% by mass). A resin composition 4 was prepared in the same manner as in Example 1 except for the above.

&Lt; Example 5: Production of Resin Composition 5 >

In Example 1, 10 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active agent equivalent approximately 216, toluene solution having a solid content of 50 mass%) was added. Resin composition 5 was produced in the same manner as in Example 1 except for the above.

&Lt; Example 6: Production of Resin Composition 6 >

In Example 1,

20 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, and a toluene solution of 65% by mass of solid content) was added to 20 parts of a naphthol type curing agent ("SN-485-60M" 25 parts of a phenolic curing agent (&quot; LA-3018-50P &quot;, manufactured by DIC Co., Ltd .; active agent equivalent weight: about 151, 2-methoxypropanol solution having a solid content of 50%), And 12 parts of a curing agent (&quot; LA-7054 &quot;, manufactured by DIC, 124 equivalents of active group and MEK solution of 60% solid content). A resin composition 6 was produced in the same manner as in Example 1 except for the above.

&Lt; Example 7: Production of Resin Composition 7 >

In Example 2,

20 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, and a toluene solution of 65% by mass of solid content) was added to 20 parts of a naphthol curing agent (SN- ), 25 parts of a phenolic curing agent (&quot; LA-3018-50P &quot;, manufactured by DIC Co., Ltd .; active agent equivalent weight: about 151, 50% solid content of 2-methoxypropanol solution) ("LA-7054" manufactured by DIC Corporation, active agent equivalent weight: 124, MEK solution having a solid content of 60%). Resin composition 7 was produced in the same manner as in Example 2 except for the above.

&Lt; Example 8: Production of Resin Composition 8 >

In Example 3,

20 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, and a toluene solution of 65% by mass of solid content) was added to 20 parts of a naphthol curing agent (SN- ) &Lt; / RTI &gt; solid content 60% MEK solution)

, 25 parts of a phenol-based curing agent ("LA-3018-50P" manufactured by DIC Corporation, active agent equivalent weight of about 151, and a 50% solids content solution) were mixed with 50 parts of a phenolic curing agent ("LA-7054" About 124, 60% solids in MEK solution). A resin composition 8 was prepared in the same manner as in Example 3 except for the above.

&Lt; Comparative Example 1: Production of comparative resin composition 1 >

In Example 1, 75 parts of spherical silica ("UFP-30" manufactured by Denki Kagakuko Co., Ltd., average particle diameter: 0.078 μm, specific surface area: 30.7 m 2 / g) was mixed with an amine series silane coupling agent (Average particle diameter 0.77 mu m, specific surface area 5.9 m2 / g, "SO-C2" manufactured by Adomex Co., Ltd.) Comparative resin composition 1 was produced in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 2: Production of comparative resin composition 2 >

75 parts of spherical silica ("UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter: 0.078 μm, specific surface area: 30.7 m 2 / g) in Example 2 was mixed with an amine series silane coupling agent (Average particle diameter 0.77 mu m, specific surface area 5.9 m2 / g, "SO-C2" manufactured by Adomex Co., Ltd.) Comparative resin composition 2 was prepared in the same manner as in Example 2 except for the above.

&Lt; Comparative Example 3: Production of comparative resin composition 3 >

In Example 6, 75 parts of spherical silica ("UFP-30" manufactured by Denki Kagakuko Co., Ltd., average particle diameter: 0.078 μm, specific surface area: 30.7 m 2 / g) was mixed with an amine series silane coupling agent (Average particle diameter 0.77 mu m, specific surface area 5.9 m2 / g, "SO-C2" manufactured by Adomex Co., Ltd.) Comparative resin composition 3 was prepared in the same manner as in Example 6 except for the above.

&Lt; Comparative Example 4: Production of comparative resin composition 4 >

75 parts of spherical silica ("UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter: 0.078 μm, specific surface area: 30.7 m 2 / g) in Example 8 was mixed with an amine series silane coupling agent (Average particle diameter 0.77 mu m, specific surface area 5.9 m2 / g, &quot; SO-C2 &quot; manufactured by Adomex Co., Ltd.). Comparative resin composition 4 was prepared in the same manner as in Example 8 except for the above.

&Lt; Comparative Example 5: Production of comparative resin composition 5 >

3 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Kagaku Co., Ltd., number average molecular weight: 20895) was mixed with 100 parts by weight of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Kagaku Co., Ltd .; MEK having a solid content of 30% by mass and cyclohexanone 1: 1 solution). Comparative resin composition 5 was prepared in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 6: Production of Comparative Resin Composition 6 >

3 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Kagaku Co., Ltd., number average molecular weight 20895) were mixed in the same manner as in Example 1 except that an ester type phenoxy resin ("YL7891BH30" manufactured by Mitsubishi Kagaku Co., Gt; 1: 1 &lt; / RTI &gt; solution). Comparative resin composition 6 was produced in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 7: Production of comparative resin composition 7 >

3 parts of a polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Kagaku Co., Ltd., number average molecular weight: 20895) was added to 100 parts by weight of an ester type phenoxy resin ("YL7891BH30" manufactured by Mitsubishi Kagaku Co., Ltd .; MEK having a solid content of 30% Gt; 1: 1 &lt; / RTI &gt; solution). Comparative resin composition 7 was prepared in the same manner as in Example 6 except for the above.

&Lt; Measurement of average particle diameter of inorganic filler &

100 g of inorganic filler, 0.1 g of dispersant ("SN9228" manufactured by Sanno Fuko Co., Ltd.) and 10 g of methyl ethyl ketone were weighed into a vial bottle and dispersed by ultrasonic wave for 20 minutes. The particle diameter distribution was measured in a batch cell system using a laser diffraction particle diameter distribution measuring apparatus ("SALD-2200" manufactured by Shimadzu Corporation), and the average particle diameter by the intermediate diameter was calculated.

&Lt; Measurement of specific surface area of inorganic filler &

The specific surface area of the inorganic filler was measured by calculating the specific surface area using a BET automatic specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Mountain Tex), adsorbing nitrogen gas on the sample surface, and using the BET multi-point method.

&Lt; Measurement of number average molecular weight of polycarbonate resin >

100 mg of each polycarbonate resin and 5 g of a dispersing agent ("N-methylpyrrolidone" manufactured by Kanto Kagaku Co., Ltd.) were weighed in a vial bottle and dispersed by ultrasonic wave for 20 minutes. (Shodex GPC-101, manufactured by Shoko Scientific Co., Ltd.) was used after filtration using a membrane filter ("ADOVANTEC" manufactured by Toyobo Co., Ltd., 0.5 μm cut) (Mn) was calculated. The results were as follows.

Number average molecular weight of &quot; FPC2136 &quot;: 20895

Number average molecular weight of &quot; FPC0220 &quot;: 18911

Number average molecular weight of &quot; T5652 &quot;: 2035

[Production of Resin Sheet]

As a support, a PET film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., hereinafter sometimes referred to as "release PET") having been subjected to release treatment with an alkyd resin releasing agent (AL- .

&Lt; Production of Resin Sheet A &

Each of the resin compositions was uniformly coated on the mold releasing PET with a die coater so that the thickness of the resin composition layer after drying was 15 占 퐉 and dried at 80 占 폚 for 3 minutes to obtain a resin composition layer on the releasing PET. Subsequently, a rough surface of a polypropylene film ("ALPAN MA-411" manufactured by Oji-Fetex Co., Ltd., thickness: 15 μm) as a protective film was laminated on the surface of the resin composition layer not bonded to the support, Respectively. Thus, a resin sheet A comprising a release PET (support), a resin composition layer, and a protective film in this order was obtained.

&Lt; Production of Resin Sheet B &

Each resin composition was uniformly coated on the mold releasing PET with a die coater so that the thickness of the resin composition layer after drying was 6 占 퐉 and dried at 80 占 폚 for 1 minute to obtain a resin composition layer on the mold releasing PET. Subsequently, a rough surface of a polypropylene film ("ALPAN MA-411" manufactured by Oji-Fetex Co., Ltd., thickness: 15 μm) as a protective film was laminated on the surface of the resin composition layer not bonded to the support, Respectively. Thus, a resin sheet B comprising a release PET (support), a resin composition layer, and a protective film in this order was obtained.

[Measurement of peel strength of copper foil]

<Production of sample>

(1) Treatment of copper foil

(Ra value = 1 mu m) was applied to the copper surface by immersing the glossy surface of "3EC-III" (electric copper foil, 35 mu m) produced by Mitsui Kinzoku Kozan Co., Ltd. in a Macro Etch bond "CZ-8101" And subjected to anti-corrosive treatment (CL8300). This copper foil is called CZ copper foil. Further, heat treatment was performed in an oven at 130 캜 for 30 minutes.

(2) Formation of laminate and insulating layer of copper foil

A protective film was peeled off from each resin sheet A prepared in Examples and Comparative Examples, and a vacuum type vacuum laminator ("MVLP-500" manufactured by Meikisha Co., Ltd.) was used. Both surfaces of the laminate were laminated so as to be bonded to an epoxy resin double-sided copper-clad laminate (thickness of copper foil: 18 mu m, thickness of substrate: 0.4 mm, &quot; R1515A &quot; The lamination treatment was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or lower, followed by pressing at 100 deg. C and a pressure of 0.74 MPa for 30 seconds. The release PET was peeled from the laminated resin sheet. On the resin composition layer, the treated surface of the CZ copper foil was laminated under the same conditions as above. Then, the resin composition layer was cured at 190 占 폚 for 90 minutes under a curing condition to form an insulating layer to prepare a sample.

&Lt; Measurement of Copper Peeling Strength (Adhesiveness 1)

The prepared sample was cut into small pieces of 150 x 30 mm. An end of a 10 mm width and 100 mm length was cut into a piece of copper foil of a small piece with a cutter and one end of the copper foil was peeled and held with a holding tool (AC-50C-SL, , And a load of 35 mm in a vertical direction at a rate of 50 mm / min at room temperature using an Instron universal testing machine was measured according to JIS C6481.

&Lt; Measurement of Copper Peeling Strength (Adhesion Property 2) after Inner Environmental Test (HAST) >

The produced sample was subjected to an accelerated environmental test under the conditions of 130 ° C and 85% RH for 100 hours using an advanced accelerated life test device ("PM422" manufactured by Kusumoto Chemical Industry Co., Ltd.). Thereafter, one end of the copper foil was peeled off and held with a holding tool (automobile tester, AC-50C-SL, manufactured by TS Seisakusho Co., Ltd.) and measured with an Instron universal testing machine at room temperature, The load at the time of peeling 35 mm in the vertical direction at a speed of 50 mm / min was measured according to JIS C6481.

Further, the case where the measurement result at the adhesion 2 was less than 0.20 kgf / cm was evaluated as &quot; X &quot;, and the case where the measurement result was 0.20 kgf / cm or more was evaluated as &quot;

[Measurement of thickness of insulating layer between conductor layers and insulation reliability of insulating layer]

(Preparation of substrate for evaluation)

(1) ground treatment of inner layer circuit board

A copper clad epoxy resin double-sided copper clad laminate (copper foil having a thickness of 3 占 퐉 and a thickness of 3 占 퐉) having circuit conductors (copper) formed on the both surfaces thereof with wiring patterns of L / S (line / space) = 2 占 퐉 / Thickness: 0.15 mm, &quot; HL832NSF LCA &quot;, manufactured by Mitsubishi Gas Kagaku Co., Ltd., size of 255 x 340 mm) was prepared. Both surfaces of the inner layer circuit board were subjected to an organic film treatment of the copper surface with &quot; FlatBOND-FT &quot;

(2) Laminate of resin sheet

The protective film was peeled off from each resin sheet B prepared in the examples and the comparative example, and the resin composition layer was bonded to the inner layer circuit board using a batch type vacuum pressure laminator (Nikkiso Materials, 2 stage buildup laminator, CVP700) Laminated on both sides of the inner layer circuit board. The laminate was subjected to pressure reduction for 30 seconds to set the air pressure to 13 hPa or less and compression bonding at 130 DEG C and a pressure of 0.74 MPa for 45 seconds. Next, hot pressing was performed at 120 DEG C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of the resin composition layer

An inner layer circuit board laminated with a resin sheet was placed in an oven at 100 캜, changed into an oven at 180 캜 for 30 minutes, and thermally cured for 30 minutes to form an insulating layer having a thickness of 5 탆, . This is referred to as substrate A.

(4) Step of performing harmonic treatment

The insulating layer of the substrate A was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:

(60 占 폚) for 5 minutes in an aqueous solution of a swelling solution ("Swelling Deep Securigant P" manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether and sodium hydroxide) and then with an oxidizing agent solution (Concentrate Compact CP (Aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 DEG C for 10 minutes and finally at 40 DEG C in a neutralizing solution ("Reduction Solution Securigant P" manufactured by Atotech Japan Co., After immersing for 5 minutes, it was dried at 80 DEG C for 15 minutes. This is referred to as a coarse substrate A.

(5) Step of forming conductor layer

(5-1) Electroless plating process

In order to form a conductor layer on the surface of the insulating layer of the coarse substrate A, a plating process (a copper plating process using a chemical solution manufactured by Atotech Japan Co., Ltd.) including the following steps 1 to 6 was performed to form a conductor layer.

1. Alkali cleaning (Cleaning and charge control of the surface of the insulating layer provided with via holes)

The surface of the coarse substrate A was cleaned using a Cleaning Cleaner Securiganth 902 (trade name) at 60 ° C for 5 minutes.

2. Soft etching (cleaning in via hole)

The surface of the coarsened substrate A was treated with an aqueous solution of sulfuric acid-oxidized peroxo 2-sodium sulfate at 30 占 폚 for 1 minute.

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

The surface of the coarsened substrate A is referred to as Pre. Dip Neoganth B (trade name) for 1 minute at room temperature.

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

The surface of the coarsened substrate A was treated with Activator Neoganth 834 (trade name) at 35 DEG C for 5 minutes.

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

The surface of the harmonizing substrate A was treated with a mixed solution 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 coarsened substrate A was treated with a solution of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name) and Reducer Cu Lt; 0 &gt; C for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 mu m.

(5-2) Electroplating process

Next, the electrolytic copper plating process was performed under the condition that copper was filled in the via hole by using the chemical solution manufactured by Atotech Japan. Thereafter, as a resist pattern for patterning by etching, a land pattern having a diameter of 1 mm, which is conducted to a via hole, and a circular conductor pattern having a diameter of 10 mm which is not connected to the lower layer conductor, A conductor layer having a land and a conductor pattern was formed. Next, annealing was performed at 200 캜 for 90 minutes. This substrate was referred to as &quot; evaluation substrate B &quot;.

&Lt; Measurement of thickness of insulating layer between conductor layers >

The evaluation substrate B was subjected to a cross-section observation using an FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology Co., Ltd.). Specifically, the cross section in the direction perpendicular to the surface of the conductor layer was cut off by a FIB (focused ion beam), and the thickness of the insulation layer between the conductor layers was measured from the cross-sectional SEM image. For each sample, five cross-sectional SEM images taken randomly were observed, and the average value is shown in the following table as the thickness (占 퐉) of the insulating layer between the conductor layers.

&Lt; Evaluation of Insulation Reliability of Insulating Layer &

The side of the circular conductor with a diameter of 10 mm of the evaluation substrate B obtained above was used as a positive electrode and the side of the lattice conductor (copper) of the inner-layer circuit board connected to a land having a diameter of 1 mm was used as a negative electrode, (Manufactured by J-RAS Co., Ltd., &quot; ECM-2200 &quot; manufactured by J-RAS Co., Ltd.) at 130 ° C under conditions of 85% relative humidity and 3.3V DC voltage, 100 &quot;). This measurement was carried out six times. When the resistance value of all the six test pieces was 10 ⁷ Ω or more, it was evaluated as "◯", and when one of them was less than 10 ⁷ Ω, "x" The resistance values are shown in the following table. The insulation resistance values shown in the following table are the lowest values of the insulation resistance values of the six test pieces.

The components used in the preparation of the resin compositions 1 to 8 and the comparative resin compositions 1 to 7 and their blending amounts are shown in the following Tables. The "content of the component (C)" in the following table represents the content (mass%) of the component (C) when the resin component is 100 mass% (Mass%) of the component (D) when the foot component is 100 mass%.

In Examples 1 to 8, even when the components (E) to (F) are not contained, it is confirmed that the results are the same as those of the above-described embodiment although the degree is different.

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 (17)

A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a polycarbonate resin, and (D)
(D) the inorganic filler has an average particle diameter of 100 nm or less. A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) a polycarbonate resin, and (D)
(D) the inorganic filler has a specific surface area of 15 m 2 / g or more. The resin composition according to Claim 1 or 2, wherein the content of the component (D) is 50% by mass or more when the content of the nonvolatile component in the resin composition is 100% by mass. The curable resin composition according to claim 1 or 2, wherein the component (B) is at least one member selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent and a carbodiimide- By weight. The resin composition according to claim 1 or 2, wherein the component (B) comprises an active ester-based curing agent. The resin composition according to claim 1 or 2, wherein the component (C) is at least one of an aliphatic skeleton-containing polycarbonate resin and an aromatic skeleton-containing polycarbonate resin. 3. The resin composition according to claim 1 or 2, wherein the component (C) has a number average molecular weight of 1,000 or more and 200,000 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 30% by mass or less when the resin component is 100% by mass. The resin composition according to claim 1 or 2, which is 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. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 11 provided on the support. The resin sheet according to claim 12, wherein the thickness of the resin composition layer is 15 占 퐉 or less. 14. The semiconductor device according to claim 12 or 13, further 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 first conductor layer and the second conductor layer Wherein the resin sheet is for forming the insulating layer of a printed wiring board having an interval of 6 占 퐉 or less. 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 11. The printed wiring board according to claim 15, wherein a distance between the first conductor layer and the second conductor layer is 6 탆 or less. A semiconductor device comprising the printed wiring board according to claim 15 or 16.

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