KR20180103754A - Resin composition layer - Google Patents

Abstract

The present invention provides a resin composition layer capable of obtaining a curing product which is excellent in adhesion to a base and reflow resistance even when a thickness is thin. The resin composition layer comprises: (A) an epoxy resin; and (B) a resin composition including a curing agent. The thickness of the resin composition layer is 15 μm or less. A transmission coefficient P of the curing product obtained by thermally curing the resin composition layer for 30 minutes and at 100°C and additionally for 30 minutes and at 180°C is 1.2 cc/m^2·mm^-1·day·atom or more and 5 cc/m^2·mm^-1·day·atom or less.

Description

Resin composition layer {RESIN COMPOSITION LAYER}

The present invention relates to a resin composition layer. Further, a resin sheet comprising the resin composition layer; And an insulating layer formed of a cured product of the resin composition layer.

In recent years, in order to achieve miniaturization of electronic devices, a further thinning of the printed wiring board is progressing, and accordingly, the wiring circuit in the inner-layer board is being made finer. For example, Patent Document 1 describes a resin sheet (adhesive film) capable of coping with fine wiring, including a support and a resin composition layer.

Japanese Patent Application Laid-Open No. 2014-36051

The present inventors have studied to thin the resin composition layer of the resin sheet in order to achieve miniaturization and thinning of the additional electronic device. However, when a thin resin composition layer is applied to the build-up use, There is a possibility that sufficient adhesion can not be ensured due to the influence.

Disclosure of the Invention A problem to be solved by the present invention is to provide a resin composition layer capable of obtaining a cured product excellent in adhesiveness and reflow resistance even when the thickness is thin; A resin sheet comprising the resin composition layer; And an insulating layer formed by using the resin composition layer, and a semiconductor device.

In order to achieve the object of the present invention, the present inventors have made intensive investigations and found that when the thickness of the resin composition layer is small, oxygen is likely to permeate into the cured product of the resin composition layer, resulting in poor adhesion. Therefore, by adjusting the transmission coefficient P of the cured product of the resin composition layer so as to be within a predetermined range, it is possible to obtain a cured product of the resin composition layer which is excellent in base adhesion and reflow resistance even if the thickness of the resin composition layer is thin Thus, the present invention has been accomplished.

That is, the present invention includes the following contents.

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

The thickness of the resin composition layer is 15 占 퐉 or less,

The resin composition layer was thermally cured at 100 占 폚 for 30 minutes and further at 180 占 폚 for 30 minutes to obtain a cured product having a transmission coefficient P of 1.2 cc / m2 占 퐉 ^-1占 day atom atom or more and 5cc / m2 占 퐉 ^-1 day atoms or less.

[2] A resin composition layer according to [1], which is for forming a wiring by a semi-additive method.

[3] A resin composition layer according to [1] or [2], which contains (C) an inorganic filler.

[4] The resin composition layer according to [3], wherein the content of the component (C) is 40% by mass or more and 80% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[5] The resin composition layer according to [3] or [4], wherein the component (C) has an average particle diameter of 0.05 μm or more and 0.35 μm or less.

[6] The resin composition layer according to any one of [1] to [5], wherein the content of the component (B) is 20% by mass or less when the content of the resin component is 100% by mass.

[7] The resin composition layer according to any one of [1] to [6], wherein the component (B) contains an active ester type curing agent.

[8] The resin composition layer according to [7], wherein the content of the active ester curing agent is 15 mass% or less when the content of the resin component is 100 mass%.

[9] A resin composition layer according to any one of [1] to [8], which contains (D) a thermoplastic resin.

[10] The resin composition layer according to [9], wherein the weight average molecular weight of the component (D) is 38000 or more.

[11] The resin composition layer according to any one of [1] to [10], wherein the transmission coefficient P is 2 cc / m 2 · mm ^-1 · day · atom or more and 4 cc / m 2 · mm ^-1 · day · atom or less.

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

[13] A resin composition layer according to any one of [1] to [12], which is for forming an interlayer insulating layer of a printed wiring board.

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

[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 layer according to any one of [1] to [13].

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

According to the present invention, it is possible to provide a resin composition layer capable of obtaining a cured product excellent in base adhesion and reflow resistance even if the thickness is thin; A resin sheet comprising the resin composition layer, a printed wiring board having an insulating layer formed using the resin composition layer, and a semiconductor device.

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

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

The "resin component" refers to a component other than the inorganic filler (C) to be described later, which is a nonvolatile component constituting the resin composition.

[Resin composition layer]

The resin composition layer of the present invention is a resin composition layer comprising a resin composition comprising (A) an epoxy resin and (B) a curing agent, wherein the thickness of the resin composition layer is 15 占 퐉 or less, is for 30 minutes, added to by 30 minutes heat cure at 180 ℃ cured product permeation coefficient P is obtained, is ^{1.2cc / ㎡ · ㎜ -1 · day} · atom more than ^{5cc / ㎡ · ㎜ -1 · day} · atom or less. By adjusting the permeation coefficient P to be within the above range, it is possible to provide a cured product excellent in adhesion to the base and reflow resistance even when the thickness of the resin composition layer is 15 탆 or less.

The thickness of the resin composition layer is 15 占 퐉 or less, preferably 13 占 퐉 or less, more preferably 10 占 퐉 or less, further preferably 8 占 퐉 or less, from the viewpoints of downsizing and reduction in thickness. 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, or the like.

The resin composition layer is formed of a resin composition comprising (A) an epoxy resin and (B) a curing agent. Setting the transmission coefficient P within the above range can be realized by adjusting each component contained in the resin composition. The resin composition may further contain additives such as (C) an inorganic filler, (D) a thermoplastic resin, (E) a curing accelerator, (F) a flame retardant and (G) an organic filler. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

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

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin , An alicyclic epoxy resin having an ester skeleton, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a glycidylamine-type epoxy resin, and an epoxy resin having a butadiene structure are preferable. Bisphenol A type epoxy resins, F type epoxy resin and cyclohexane type epoxy resin are more preferable. 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 resin), 630LSD " (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone, or two or more kinds may be used in combination.

Examples of the solid epoxy resin include epoxy resins such as bicalcylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, Epoxy resins such as phenylene type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin and tetraphenyl ethane type epoxy resin are preferable, and biscylenol type epoxy resin, Bisphenol AF type epoxy resin, and naphthylene ether type epoxy resin are 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 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: 2 to 1:10, : 5 to 1:10 is more preferable.

From the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, the content of the component (A) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more % Or more, more preferably 30 mass% or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 60 mass% or less, more preferably 55 mass% or less, 50 mass% or less, or 45 mass% or less.

The epoxy equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. 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 polystyrene reduced weight average molecular weight 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. 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" SN395 "," SN395 "," SN395 "," SN395 "," SN395 "," SN395 "," SN395 "," SN395 "," TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "and" EXB-9500 "

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 prepolymers. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (multifunctional cyanate ester resin), "BA230 BA230S75 " (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 amount ratio 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: 1.5, in the ratio of [the total number of epoxy groups of epoxy resin]: [the total number of reactors of the curing agent] More preferably 1: 0.1 to 1: 1. 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.

In one embodiment, the resin composition includes the above-mentioned epoxy resin and a curing agent. The resin composition comprises (A) a mixture of a liquid epoxy resin and a solid epoxy resin as the epoxy resin, and (B) a mixture of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent and a cyanate ester- It is preferable to include at least one kind selected. The mass ratio of the mixture of the liquid epoxy resin and the solid epoxy resin as the epoxy resin (A) (liquid epoxy resin: solid epoxy resin) is preferably from 1: 0.1 to 1:20, more preferably from 1: 1 to 1:10 , More preferably from 1: 5 to 1: 8. As the curing agent (B), at least one selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent and a cyanate ester-based curing agent is preferable, and a group consisting of a phenolic curing agent and an active ester- And more preferably at least one selected from the group consisting of

As the component (B), it is preferable to contain an active ester-based curing agent from the viewpoint of improving chemical resistance. The content of the active ester curing agent is preferably 15% by mass or less, more preferably 14% by mass or less, more preferably 14% by mass or less, more preferably 10% by mass or less, And more preferably 13 mass% or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more.

The content of the active ester curing agent in the entirety of the component (B) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, relative to 100% Or more. The upper limit is preferably 75 mass% or less, more preferably 73 mass% or less, further preferably 70 mass% or less. By including the active ester type curing agent so as to be in such a range, it becomes easy to adjust the permeation coefficient P within a predetermined range.

The content of the component (B) is preferably 20 mass% or less, more preferably 19 mass% or less, further preferably 18 mass% or less, when the resin component is 100 mass%. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more. By making the content of the component (B) fall within this range, it is possible to effectively improve the base adhesion.

- (C) Inorganic filler -

In one embodiment, the resin composition may contain an inorganic filler. The material of the inorganic filler is not particularly limited and may be, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Aluminum hydroxide, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, , Barium titanate 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 is preferably 0.35 占 퐉 or less, more preferably 0.3 占 퐉 or less, still more preferably 0.25 占 퐉 or less from the viewpoint of increasing the surface area of the inorganic filler and adjusting the transmission coefficient P within a predetermined range , Not more than 0.2 탆, not more than 1.5 탆, or not more than 1 탆. The lower limit of the average particle diameter is preferably 0.05 mu m or more, more preferably 0.06 mu m or more, and still more preferably 0.07 mu m or more. As the upper limit of the average particle diameter, a commercially available product of an inorganic filler having such an average particle diameter is, for example, " UFP-30 " manufactured by Denki Kagaku Kogyo Co.,

The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured with a laser diffraction scattering type particle size distribution measuring apparatus, and the average particle size can be measured with the intermediate diameter thereof. 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 size distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd., "SALD-2200" manufactured by Shimadzu Corporation can be used.

The specific surface area of the inorganic filler is preferably not less than 15 m 2 / g, more preferably not less than 20 m 2 / g, and still more preferably not less than 25 m 2 / g, from the viewpoint of adjusting the transmission coefficient P within a predetermined range. The upper limit of the specific surface area is preferably 60 m 2 / g or less, more preferably 50 m 2 / g or less, and still more preferably 40 m 2 / g or less. The specific surface area of the inorganic filler can be measured by using, for example, a BET automatic specific surface area measuring device or the like. More specifically, the specific surface area is determined by adsorbing nitrogen gas on the surface of the sample 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 .

The inorganic filler is preferably at least one 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, It is preferably treated with at least one kind of surface treating agent such as a quinic acid compound, a quinic acid compound, a quinic acid compound, a quinic acid compound, a quinic acid compound, a quinic acid compound, a titanate-based coupling agent and the like and is particularly preferably treated with an aminosilane 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.

From the viewpoint of improving the dispersibility of the inorganic filler, the surface treatment by the surface treatment agent is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent per 100 parts by mass of the component (C) To 3 parts by mass, more preferably 0.3 part by mass to 2 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.

When the resin composition contains the component (C), the content of the inorganic filler is preferably 40 mass% or less, more preferably 40 mass% or less when the nonvolatile component in the resin composition is 100 mass% from the viewpoint of adjusting the transmission coefficient P within a predetermined range % Or more, more preferably 45 mass% or more, and further preferably 50 mass% or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 70% by mass or less, from the viewpoints of improving the insulating performance and the balance of physical properties of the resin composition layer and improving the base adhesion. Is 60 mass% or less, or 55 mass% or less.

- (D) Thermoplastic resin -

In one embodiment, the resin composition may contain (D) a thermoplastic resin. 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, polycarbonate resins, polyether ether ketone resins, and polyester resins, and phenoxy resins are preferred. The thermoplastic resin may be used singly or in combination of two or more kinds.

The polystyrene reduced weight average molecular weight of the thermoplastic resin is preferably 38000 or more, more preferably 40,000 or more, and even more preferably 42000 or more, from the viewpoint of lowering the transmission coefficient P. [ The upper limit is preferably not more than 100000, more preferably not more than 70000, still more preferably not more than 60,000. The polystyrene reduced weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K- 804L as a mobile phase and chloroform as a mobile phase at a column temperature of 40 ° C and using a calibration curve of standard polystyrene.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resins may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" Phenone skeleton-containing phenoxy resin). In addition, "FX280" and "FX293" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" YL7769BH30 "," YL6794 "," YL7213 "," YL7290 ", and" YL7482 ".

As the polyvinyl acetal resin, for example, a polyvinyl formal resin and a polyvinyl butyral resin can be mentioned, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, "Denkabutilal 4000-2", "Denkabutilal 5000-A", "Denkabutilal 6000-C", "Denkabutilal (For example, BX-5Z), KS series (for example, KS-1), BL series and BM series manufactured by Sekisui Chemical Co., Ltd. .

Specific examples of the polyimide resin include "Rika coat SN20" and "Rika coat PN20" manufactured by Shin-Nippon Rikagaku. Specific examples of the polyimide resin include linear polyimide (polyimide described in JP-A No. 2006-37083) obtained by reacting bifunctional hydroxyl-terminated polybutadiene, diisocyanate compound and tetrabasic acid anhydride, polysiloxane And modified polyimides such as skeleton-containing polyimide (Japanese Unexamined Patent Application Publication No. 2002-12667 and Japanese Unexamined Patent Publication No. 2000-319386, etc.).

Specific examples of the polyamide-imide resin include " viromax HR11NN " and " viromax HR16NN " manufactured by Toyobo Co., Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) produced by Hitachi Kasei Corporation.

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

Specific examples of the polyphenylene ether resin include an oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Kagaku Co., Ltd. and the like.

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

Among them, a phenoxy resin and a polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in a preferred embodiment, the thermoplastic resin includes at least one selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Among them, a phenoxy resin is preferable as the thermoplastic resin, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable. By using a phenoxy resin having a weight average molecular weight of 40,000 or more, the transmittance coefficient P is reduced, and even if the insulating layer is thin, the surface roughness can be stably formed.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, Or more. The upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 2 mass% or less. By making the content of the component (D) fall within this range, the transmittance coefficient P is reduced, and even if the insulating layer is thin, the surface roughness can be stably formed.

- (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, imidazole-based curing accelerators and metal-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, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) -Diazabicyclo (5,4,0) undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferred.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline An imidazole compound and an adduct of an imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, for example, " P200-H50 " 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 ] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1 , 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and 1- (o-tolyl) , 1,5,7-triazabicyclo [4.4.0] deca-5-ene.

Examples of the metal-based curing accelerator include organometallic 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) 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, still more preferably 0.1% by mass or more, Or more. The upper limit is preferably 3 mass% or less, more preferably 2 mass% or less, further preferably 1 mass% or less. When the content of the curing accelerator is within this range, it is easy to improve the adhesion of the base.

- (F) Flame retardant -

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

As the flame retardant, a commercially available product may be used, for example, "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 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, in the case where the nonvolatile component in the resin composition is 100% , And more preferably 0.5% by mass to 10% by mass.

- (G) Organic filler -

In one embodiment, the resin composition may contain (G) an organic filler. By containing the component (G), the tensile fracture strength of the cured product of the resin composition layer of the resin sheet can be improved. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicon particles.

As the rubber particles, a commercially available product may be used, for example, "EXL2655" manufactured by Dow Chemical Co., Ltd., "AC3401N" manufactured by Aikoko Co., Ltd., and "AC3816N".

When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, based on 100% by mass of the nonvolatile component in the resin composition , More preferably 0.3 mass% to 5 mass%, or 0.5 mass% to 3 mass%.

- (H) optional additives -

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

≪ Properties and Uses of Resin Composition Layer >

The coefficient of permeability P of the cured product obtained by thermally curing the resin composition layer at 100 占 폚 for 30 minutes and further at 180 占 폚 for 30 minutes is preferable because it is easy to balance the physical properties of the resin composition and to improve the adhesion of the resin composition to 1.2 and ^{cc / ㎡ · ㎜ -1 · day} · atom or more, preferably 1.5cc / ㎡ · more preferably ㎜ ^-1 · day · atom or more, ^{2cc / ㎡ · ㎜ -1 · day} · atom or higher. The art the upper limit of the permeability coefficient P is, and difficult to oxygen permeation in the insulating layer, and as a result, from the viewpoint of the metal oxides, such as to a copper foil of the insulating layer is suppressed, and not improving the adhesion, 5cc / ㎡ · ㎜ ^{- 1} · day · atom or less, preferably 4.5 cc / m 2 · mm ^-1 · day · atom or less, and more preferably 4 cc / m 2 · mm ^-1 · day · atom or less. The transmission coefficient P can be set within such a range by adjusting the content of the curing agent, the inorganic filler, and the thermoplastic resin, for example. The permeation coefficient P can be measured according to the description of " Measurement of Oxygen Permeability and Permeation Coefficient "

The oxygen permeability of the cured product obtained by thermally curing the resin composition layer at 100 占 폚 for 30 minutes and further at 180 占 폚 for 30 minutes is preferably such that the balance of the physical properties of the resin composition is good when the thickness of the cured product is measured to be 60 占 퐉 M 2 · day · atom or more, more preferably 25 cc / m 2 · day · atom or more, and still more preferably 30 cc / m 2 · day · atom or more. The upper limit of the oxygen permeability is preferably 80 cc / m < 2 > / day from the viewpoint of preventing oxygen from penetrating into the insulating layer and consequently inhibiting oxidation of metal such as copper foil,揃 atom, more preferably not more than 75 cc / m 2 揃 day 揃 atom, still more preferably not more than 70 cc / m 2 揃 day atom. The oxygen permeability can be measured according to the description of &quot; Measurement of Oxygen Permeability and Permeation Coefficient &quot;

The cured product obtained by thermosetting the resin composition layer at 100 占 폚 for 30 minutes and further at 180 占 폚 for 30 minutes has a transmission coefficient P of 1.2 cc / m2 占 퐉 ^-1占 day atom atom or more and 5 cc / m2 占 퐉 ^-1 · Day · atom, it exhibits excellent peel strength (base adhesion) with the copper foil. That is, an insulating layer having excellent adhesion to the substrate. The base adhesion is a load necessary for peeling a small piece having a width of 10 mm, preferably 0.2 kgf or more, more preferably 0.25 kgf or more, and further preferably 0.3 kgf or more. The upper limit is preferably 1 kgf or less, 10 kgf or less, and the like. The base adhesion can be measured according to the description of &quot; Measurement of adhesion of the base &quot;

The cured product obtained by thermally curing the resin composition layer at 100 占 폚 for 30 minutes and further at 180 占 폚 for 30 minutes exhibits excellent reflow resistance. That is, an insulating layer having excellent reflow resistance. It is preferable that the insulation layer formed by using the resin composition layer is peeled off between the insulation layer and the conductor layer at two or less positions even if the reflow process for reproducing the reflow temperature at the peak temperature of 260 DEG C is performed 20 times or more, It is more preferable that there is no peeling between the conductor layers. The reflow resistance can be evaluated according to the method described in &quot; Evaluation of reflow resistance &quot;

The resin composition layer of the present invention forms an insulating layer (cured product of the resin composition layer) excellent in adhesion to the substrate and reflow resistance even if the thickness is as small as 15 탆 or less. Therefore, the resin composition layer of the present invention can be suitably used as a resin composition for forming an insulating layer included in an electronic component. For example, a resin composition layer for forming wiring by a semi-additive process (a semi-additive process (For forming a wiring by the above-mentioned method). The resin composition layer can be suitably used as a resin composition layer (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 composition layer for forming an interlayer insulating layer of a printed wiring board (A resin composition layer for an interlaminar insulating layer of a printed wiring board).

The resin composition of the present invention can also be suitably used as a resin composition for forming a conductor layer (a resin composition for forming an insulating layer for forming a conductor layer). Further, a resin composition for sealing electronic members can also be suitably used. For example, the resin composition can be suitably used as a resin composition (a resin composition for forming a sealing layer of a semiconductor chip) for sealing a semiconductor chip.

[Resin sheet]

The resin sheet of the present invention comprises a support and a resin composition layer of the present invention formed on the support. The resin composition layer is as described in [resin composition layer].

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

When a metal foil is used as 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 copper metal may be used, or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) good.

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; Lumirror T60 &quot; manufactured by Toray Industries, Inc., &quot; Purex &quot; manufactured by Teijin Co., and &quot; Unipyl &quot;

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.

[Printed circuit board]

The printed wiring board of the present invention includes a first conductor layer, a second conductor layer, and an insulating layer. The insulating layer contains a resin composition containing (A) an epoxy resin and (B) a curing agent and has a thickness of 15 탆 or less and is thermally cured at 100 캜 for 30 minutes and further at 180 캜 for 30 minutes to obtain a cured product the permeability coefficient _{P, 1.2cc / ㎡ · ㎜ -1} · day · atom more than ^{5cc / ㎡ · ㎜ -1 · day} · atom or less is a cured product of the resin composition layer. 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).

In a preferred embodiment, the insulating layer is formed by a cured product of the resin composition layer in the resin sheet of the present invention.

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

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

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

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

The 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 from the support side to the inner layer substrate. Examples of the member for heating and pressing the resin sheet to the inner layer substrate (hereinafter also referred to as &quot; hot pressing member &quot;) include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). Further, it is preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the inner layer substrate, instead of directly pressing the heat-press member to the resin sheet.

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. As a commercially available vacuum laminator, for example, vacuum pressurized laminator manufactured by Meikishesakusho Co., Ltd., plastic applicator manufactured by Nikko Materials Co., Ltd., and batch vacuum pressurized laminator can be given.

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

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

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

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

For example, 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 in the range of 120 to 240 占 폚 (preferably in the range of 150 to 220 占 폚, more preferably 170 占 폚 To 200 占 폚), and the curing time may be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

The resin composition layer may be preheated 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 (V) the step of forming the conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. When the support is removed after the step (II), the removal of the support is carried out between the step (II) and the step (III), between the step (III) and the step (IV) ). If necessary, the multilayer wiring board may be formed by repeatedly forming the insulating layer and the conductor layer of the process (II) to the process (V). In this case, it is preferable that the thickness of the insulating layer (t1 in Fig. 1) between the respective conductor layers is within the above range.

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, the swelling treatment by the swelling liquid, the coarsening treatment by the oxidizing agent, and the neutralization treatment by the neutralizing liquid can be carried out in this order to coarsen 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 can be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated 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 a neutralizing solution used for harmonization treatment, and commercially available products include, for example, &quot; Reduction Solution Securement G P manufactured by Atotech Japan Co. &quot;. 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 . The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper- Alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer or nickel-chromium alloy, copper-nickel alloy, An alloy layer of copper-titanium alloy is preferable and an alloy layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer or nickel-chromium alloy is more preferable, Do.

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

The thickness of the conductor layer 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-additive method or a full additive method. In view of simplicity of manufacture, It is preferably formed by the additive method. Hereinafter, the conductor layer is formed by the semi-additive method.

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 have 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 more 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; Measurement of average particle diameter of inorganic filler &

100 g of inorganic filler, 0.1 g of dispersant ("SN9228" manufactured by Sanofucco) and 10 g of methyl ethyl ketone were weighed into a vial bottle and dispersed by ultrasonic wave for 20 minutes. The particle size distribution was measured in a batch cell system using a laser diffraction particle size 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 adsorbing nitrogen gas on the surface of the sample and calculating the specific surface area using the BET multi-point method using a BET automatic specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountain Tex).

<Used inorganic filler>

Inorganic filler 1: 100 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 added N-phenyl-3-aminopropyltrimethoxysilane Manufactured by Shin-Etsu Chemical Co., Ltd., KBM573).

Inorganic filler 2: 100 parts of spherical silica (&quot; SC2500SQ &quot; manufactured by Adomex Co., Ltd., average particle diameter: 0.77 mu m, specific surface area: 11.2 m2 / g) was added N-phenyl-3-aminopropyltrimethoxysilane Manufactured by Kokusa Kogyo Co., Ltd., KBM573).

<Preparation of Resin Composition 1>

, 6 parts of a biscylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: about 185), 5 parts of a naphthalene type epoxy resin (ESN475V manufactured by Shin Nitetsu Sumikin Kagaku, epoxy equivalent weight of about 332) , 15 parts of a resin ("YL7760" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent of about 238), 2 parts of cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent weight of 135), phenoxy resin ("YX7553BH30 2 parts of a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass, Mw = 35000) were dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, 4 parts of a triazine skeleton-containing cresol novolac curing agent (&quot; LA-3018-50P &quot;, manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 50% solids content of 2-methoxypropanol solution) , 6 parts of an active ester type curing agent ("EXB-8150-65T" manufactured by DIC Corporation, active group equivalent of about 229, and a toluene solution of a nonvolatile component of 65% by mass), 50 parts of inorganic filler 1 and 50 parts of an amine curing accelerator Pyridine (DMAP)) were uniformly dispersed in a high-speed rotary mixer and then filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO Co., Ltd.) to prepare Resin Composition 1.

<Preparation of Resin Composition 2>

, 6 parts of a biscylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: about 185), 5 parts of a naphthalene type epoxy resin (ESN475V manufactured by Shin Nitetsu Sumikin Kagaku, epoxy equivalent weight of about 332) 15 parts of a resin ("YL7760" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent of about 238), 15 parts of a bisphenol epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: about 169, bisphenol A type and bisphenol F type , 2 parts of naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent of 213), 2 parts of phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Kagaku Co., 2 parts of a 1: 1 solution of hexane: methyl ethyl ketone (MEK), Mw = 44000) was dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone while stirring. After cooling to room temperature, 4 parts of a triazine skeleton-containing cresol novolac curing agent (&quot; LA-3018-50P &quot;, manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 50% solids content of 2-methoxypropanol solution) 6 parts of an active ester type curing agent ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent of about 220, 65% by mass of a nonvolatile component of MEK solution), 40 parts of inorganic filler 1 and 40 parts of an amine curing accelerator Pyridine (DMAP)) were uniformly dispersed in a high-speed rotary mixer and then filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO Co., Ltd.) to prepare Resin Composition 2.

<Preparation of Resin Composition 3>

, 6 parts of a biscylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: about 185), 5 parts of a naphthalene type epoxy resin (ESN475V manufactured by Shin Nitetsu Sumikin Kagaku, epoxy equivalent weight of about 332) 15 parts of a resin ("YL7760" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent of about 238), 15 parts of a bisphenol epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: about 169, bisphenol A type and bisphenol F type , 2 parts of naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent of 213), 2 parts of phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Kagaku Co., 2 parts of a 1: 1 solution of hexane: methyl ethyl ketone (MEK), Mw = 44000) was dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone while stirring. After cooling to room temperature, 4 parts of a triazine skeleton-containing cresol novolac curing agent (&quot; LA-3018-50P &quot;, manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 50% solids content of 2-methoxypropanol solution) , 12 parts of an active ester type curing agent ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent of about 220, 65% by mass of a nonvolatile component of MEK solution), 40 parts of inorganic filler 1, 40 parts of an amine curing accelerator Pyridine (DMAP)) were uniformly dispersed in a high-speed rotary mixer and then filtered through a cartridge filter ("SHP020", manufactured by ROKITECHNO Co., Ltd.) to prepare Resin Composition 3.

<Preparation of Resin Composition 4>

, 6 parts of a biscylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: about 185), 5 parts of a naphthalene type epoxy resin (ESN475V manufactured by Shin Nitetsu Sumikin Kagaku, epoxy equivalent weight of about 332) , 15 parts of a resin ("YL7760" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent of about 238), 2 parts of cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent weight of 135), phenoxy resin ("YX7553BH30 , 2 parts of cyclohexanone: methyl ethyl ketone (MEK) in a solid content of 30% by mass) was dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, 4 parts of a triazine skeleton-containing cresol novolac curing agent (&quot; LA-3018-50P &quot;, manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 50% solids content of 2-methoxypropanol solution) 6 parts of an active ester type curing agent ("EXB-8000L-65M" manufactured by DIC Corporation, active agent equivalent of about 220, 65% by mass of a nonvolatile component of MEK solution), 160 parts of inorganic filler 2, Pyridine (DMAP)) were uniformly dispersed in a high-speed rotary mixer, followed by filtration through a cartridge filter ("SHP020" manufactured by ROKITECHNO Co., Ltd.) to prepare Resin Composition 4.

The components used in the preparation of the resin compositions 1 to 4 and the compounding amount thereof (parts by mass of nonvolatile matter) are shown in the following table. The abbreviations and the like in the following table are as follows.

Content of the curing agent: The content of the curing agent when the resin component in the resin composition is 100% by mass

Content of active ester-based curing agent: Content of active ester-based curing agent when the resin component in the resin composition is 100 mass%

Content of inorganic filler: The content of the inorganic filler when the nonvolatile component in the resin composition is 100 mass%

<Production of Resin Sheet>

(Lamier R80, thickness 38 占 퐉, softening point 130 占 폚, "release PET" manufactured by Toray Industries, Inc.) which had been subjected to release treatment with an alkyd resin-based release agent ("AL-5"

Each resin composition was uniformly coated on the release PET with a die coater so that the thickness of the resin composition layer after drying was 10 占 퐉 and dried at 70 占 폚 and 95 占 폚 for 2 minutes to obtain a resin composition layer on the releasing PET. Subsequently, a roughened 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 sheet not bonded to the support to be laminated with the resin composition layer. Thus, a resin sheet A made up of a release PET (support), a resin composition layer, and a protective film in this order was obtained.

Resin sheet B was obtained in the same manner as resin sheet A except that each resin composition was uniformly coated with a die coater so that the thickness of the resin composition layer after drying was 30 占 퐉.

&Lt; Measurement of thickness of resin composition layer &

The thickness was measured using a contact type film thickness meter (MCD-25MJ, manufactured by Mitsutoyo Corporation).

&Lt; Evaluation of reflow resistance >

- Preparation of evaluation substrate A -

(1) Copper clad laminate

As the copper-clad laminate, a glass cloth base epoxy resin double-side copper-clad laminate (HL832NSF LCA, thickness: 3 mu m, substrate thickness 0.15 mm, manufactured by Mitsubishi Gas Kagaku Co., Ltd., size 255 x 340 mm) .

(2) Laminate of resin sheet

The protective film was peeled off from each of the resin sheets A prepared in Examples and Comparative Examples and the resin composition layer was bonded to the copper clad laminate by using a batch type vacuum pressure laminator (Nikkiso Materials, Ltd., 2 stage buildup laminator, CVP700) Laminated on both sides of the copper clad laminate. 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. Then, 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

The copper-clad laminate in which the resin sheet was laminated was placed in an oven at 100 캜, transferred to an oven at 180 캜 for 30 minutes, and then thermally cured for 30 minutes to form an insulating layer. This is referred to as a cured substrate A.

(4) Step of performing harmonic treatment

The insulating layer of the cured 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 10 minutes and then with an oxidizing agent solution ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) was added to a swelling solution ("Swelling Deep Securigant P" manufactured by Atotech Japan Inc., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) (Aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 DEG C for 20 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) including the following steps 1 to 6 was performed to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer on which the via hole is formed)

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 sulfuric acid peroxodisulfate solution 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 was treated for 1 minute at room temperature using Pre.Dip Neoganth B (trade name).

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 harmony substrate A was treated with a mixture solution of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name) and Reducer Cu For 15 minutes. The thickness of the electroless copper plated layer formed was 1 占 퐉.

After the electroless copper plating process, electrolytic copper plating was performed to form an electroplated copper plated layer (conductor layer) having a thickness of 14 탆 (total thickness with the electroless copper plated layer was about 15 탆). This is referred to as evaluation substrate A.

- Evaluation of reflow resistance -

The evaluation substrate A was cut with a test piece of 100 mm x 100 mm. The obtained test piece was subjected to a reflow apparatus ("HAS6116" manufactured by Anthos Co., Ltd.) was used, and IPC / JEDEC J-STD-020C ("Moisture / Reflow Sensitivity Classification for Nonhermetic Solid State Surface Mount Devices" The simulated reflow process was repeated 20 times with the described reflow temperature profile (profile for lead-free assembly; peak temperature 260 占 폚). Then, the reflow resistance was evaluated according to the following evaluation criteria.

Evaluation standard:

&Amp; cir &amp;: Peeling between the insulating layer and the conductor layer was 2 or less

X: Peeling between the insulating layer and the conductor layer occurred at three or more places

&Lt; Measurement of adhesion of base &

(1) Treatment of copper foil

(Ra value = 1 mu m) was performed on the copper surface by immersing the glossy surface of "3EC-III" (electric field copper foil, 35 mu m) manufactured by Mitsui Kinzoku Kozan Co., Ltd. into Maclech etch bond "CZ-8101" , And anti-rust treatment (CL8300). This copper foil is called a CZ copper foil. Further, it was heat-treated in an oven at 130 캜 for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer

The protective film was peeled off from each resin sheet A prepared in the examples and the comparative examples, and a vacuum vacuum laminator ("MVLP-500" manufactured by Meikisha) was used, and the inner layer Both sides of the circuit board were laminated. 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. After the lamination, the releasing PET of the supporting chain was peeled off. The treated surface of the CZ copper foil of &quot; 3EC-III &quot; was laminated on the resin composition layer on which the support was peeled under the same conditions as above. Then, the resin composition layer was cured at 190 DEG C for 90 minutes under a curing condition to form an insulating layer, thereby preparing a sample.

(3) Measurement of copper peel strength (base adhesion)

The prepared sample was cut into small pieces of 150 x 30 mm. One end of the copper foil was peeled off and held with a picking tool (AC-50C-SL, automobile tester manufactured by TS Industries Co., Ltd.) Using an Instron universal testing machine, the load when peeling 35 mm in the vertical direction at a rate of 50 mm / min at room temperature was measured according to JIS C6481 and evaluated according to the following criteria.

Evaluation standard

?: The result of measurement of the adhesion of the undergarment was not less than 0.2 kgf

X: The result of measurement of the base adhesion was less than 0.2 kgf

&Lt; Measurement of Oxygen Permeability and Permeation Coefficient >

- Production of cured sheet -

A protective film was peeled from each of the resin sheets B prepared in the examples and the comparative examples, and a batch type vacuum press laminator (Niko Materials, Ltd., 2 stage buildup laminator, CVP700) was used. Two resin Sheet B was laminated. 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. Then, the releasing PET on one side was peeled off, the resin composition layer was cured at 90 deg. C for 90 minutes, and the releasing PET on the other side was peeled off to prepare a cured sheet B.

- Measurement of Oxygen Permeability and Permeation Coefficient -

(Manufactured by MOCON CO., LTD., OX-TRAN2 / 21) in accordance with JIS-K7126 (equivalent pressure method) under an atmosphere of 23 DEG C and 0% The oxygen permeability of B was measured. RH is relative humidity. Further, based on the oxygen permeability of the cured sheet B, the permeation coefficient P (oxygen permeability coefficient P) was calculated by dividing the thickness by the thickness.

The permeability coefficient P is a ^{5.0cc / ㎡ · ㎜ -1 · day} · atom or less, "○", in the case where the transmission coefficient P is more than ^{5.0cc / ㎡ · ㎜ -1 · day} · atom was evaluated as "×" . In addition, the transmission coefficient, if P is not less than ^{1.2cc / ㎡ · ㎜ -1 · day} · atom "○", the transmission factor P is ^{1.2cc / ㎡ · ㎜ -1 · day} · atom is less than was evaluated as "×" .

In Examples 1 and 2, even when the components (C) to (E) 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 Overall thickness of the insulating layer

Claims (16)

(A) an epoxy resin, and (B) a curing agent,
The thickness of the resin composition layer is 15 占 퐉 or less,
The resin composition layer was thermally cured at 100 占 폚 for 30 minutes and further at 180 占 폚 for 30 minutes to obtain a cured product having a permeation coefficient P of 1.2 cc / m2 占 퐉 ^-1占 · atom atom or more and 5 cc / m2 占 퐉 ^-1占 day · Atom or less. The resin composition layer according to claim 1, wherein the resin composition layer is for forming a wiring by a semi-additive process. The resin composition layer according to claim 1, which further comprises (C) an inorganic filler. The resin composition layer according to claim 3, wherein the content of the component (C) is 40% by mass or more and 80% by mass or less when the content of the nonvolatile component in the resin composition is 100% by mass. The resin composition layer according to claim 3, wherein the component (C) has an average particle diameter of 0.05 탆 or more and 0.35 탆 or less. The resin composition layer according to claim 1, wherein the content of the component (B) is 20 mass% or less when the content of the resin component is 100 mass%. The resin composition layer according to claim 1, wherein the component (B) contains an active ester-based curing agent. The resin composition layer according to claim 7, wherein the content of the active ester curing agent is 15 mass% or less when the content of the resin component is 100 mass%. The resin composition layer according to claim 1, which further comprises (D) a thermoplastic resin. The resin composition layer according to claim 9, wherein the component (D) has a weight average molecular weight of 38000 or more. The resin composition layer according to claim 1, wherein the transmittance coefficient P is not less than 2 cc / m 2 · mm ^-1 · day · atom and not more than 4 cc / m 2 · mm ^-1 · day · atom. The resin composition layer according to claim 1, which is for forming an insulating layer of a printed wiring board. The resin composition layer according to claim 1, which is for forming an interlayer insulating layer of a printed wiring board. A resin sheet comprising a support and a resin composition layer according to any one of claims 1 to 13 formed on the support. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
Wherein the insulating layer is a cured product of the resin composition layer according to any one of claims 1 to 13. A semiconductor device comprising the printed wiring board according to claim 15.

Images