JP6866858B2 - Resin composition layer - Google Patents

Description

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

In recent years, in order to achieve miniaturization of electronic devices, the printed wiring board has been further reduced in thickness, and along with this, the wiring circuit in the inner layer substrate has been miniaturized. For example, Patent Document 1 describes a resin sheet (adhesive film) that includes a support and a resin composition layer and is compatible with fine wiring.

Japanese Unexamined Patent Publication No. 2014-36051

The present inventors have been studying thinning the resin composition layer of the resin sheet in order to further reduce the size and thickness of the electronic device, but applied the thin resin composition layer to the build-up application. In this case, it was found that sufficient adhesion may not be secured due to the influence of the high temperature environment when mounting the semiconductor chip.

An object of the present invention is a resin composition layer capable of obtaining a cured product having excellent substrate adhesion and reflow resistance even if the thickness is thin; a resin sheet containing the resin composition layer; using the resin composition layer. It is an object of the present invention to provide a printed wiring board provided with a formed insulating layer, and a semiconductor device.

As a result of diligent studies by the present inventors in order to achieve the object of the present invention, when the thickness of the resin composition layer is thin, oxygen easily permeates into the cured product of the resin composition layer, and as a result, adhesion is achieved. Was found to be inferior. Therefore, by adjusting the permeability coefficient P of the cured product of the resin composition layer so as to be within a predetermined range, even if the thickness of the resin composition layer is thin, the resin composition is excellent in base adhesion and reflow resistance. They have found that a cured product of a physical layer can be obtained, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition layer containing (A) an epoxy resin and (B) a resin composition containing a curing agent.
The thickness of the resin composition layer is 15 μm or less,
The permeation coefficient P of the cured product obtained by thermally curing the resin composition layer at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is 1.2 cc / m ² · mm ^-1 · day · atom or more 5 cc /. A ^{resin composition layer having m 2} · mm ^-1 · day · atom or less.
[2] The resin composition layer according to [1], which is used for forming wiring by a semi-additive method.
[3] The 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 non-volatile component in the resin composition is 100% by mass.
[5] The resin composition layer according to [3] or [4], wherein the average particle size of the component (C) is 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 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-based curing agent.
[8] The resin composition layer according to [7], wherein the content of the active ester-based curing agent is 15% by mass or less when the resin component is 100% by mass.
[9] The 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 38,000 or more.
[11] permeability coefficient P ^is not more than ^{2cc / m 2 · mm -1 ·} day · atom or ^{4cc / m 2 · mm -1 ·} day · atom, according to any one of [1] to [10] Resin composition layer.
[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] The resin composition layer according to any one of [1] to [12], which is used for forming an interlayer insulating layer of a printed wiring board.
[14] A resin sheet comprising a support and the resin composition layer according to any one of [1] to [13] provided on the support.
[15] A printed wiring board including 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 printed wiring board which is a cured product of the resin composition layer according to any one of [1] to [13].
[16] A semiconductor device including the printed wiring board according to [15].

According to the present invention, a resin composition layer capable of obtaining a cured product having excellent substrate adhesion and reflow resistance even if the thickness is thin; a resin sheet containing the resin composition layer; using the resin composition layer. A printed wiring board having a formed insulating layer and a semiconductor device can be provided.

FIG. 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 of the non-volatile components constituting the resin composition, excluding the (C) inorganic filler described later.

[Resin composition layer]
The resin composition layer of the present invention is a resin composition layer containing (A) an epoxy resin and (B) a resin composition containing a curing agent, and the thickness of the resin composition layer is 15 μm or less, and the resin composition. The permeation coefficient P of the cured product obtained by thermosetting the material layer at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is 1.2 cc / m ² · mm ^-1 · day · atom or more 5 cc / m ^2. -Mm ^-1 , day, atom or less. By adjusting the permeability coefficient P so as to be within the above range, it is possible to impart a cured product having excellent substrate adhesion and reflow resistance even if the thickness of the resin composition layer is 15 μm or less.

The thickness of the resin composition layer is 15 μm or less, preferably 13 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, from the viewpoint of miniaturization and thinning. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

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

-(A) Epoxy resin-
The resin composition contains (A) epoxy resin. Examples of the epoxy resin include bixilenol 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, and trisphenol type epoxy resin. Naftor novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type Examples thereof include epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. The epoxy resin 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 non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition includes a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “solid epoxy resin”). It is preferable to include them in combination. 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, the 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 novolac type epoxy resin, and ester skeleton. Alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, and cyclohexane type epoxy are preferable. Resin is more preferred. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL", "825", and "Epicoat" manufactured by Mitsubishi Chemical Corporation. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 "," 630LSD "(glycidylamine type epoxy resin) , "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" manufactured by Nagase ChemteX Co., Ltd. (glycidyl ester type epoxy resin), manufactured by Daicel Co., Ltd. "Ceroxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl) manufactured by Nippon Steel & Sumitomo Metal Corporation. Cyclohexane type epoxy resin), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and bixilenol type epoxy resin, naphthalene 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), and "N-690" manufactured by DIC. Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA-7311" , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayakusha ( Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. , "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "YL7800" (fluoren) Type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), the amount ratio (liquid epoxy resin: solid epoxy resin) of them is in the range of 1: 1 to 1:20 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) when used in the form of a resin sheet, appropriate adhesiveness is provided, and ii) when used in the form of a resin sheet. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more in the range of 1: 2 to 1:10 in terms of mass ratio. The range of 1: 5 to 1:10 is preferable, and the range of 1: 5 to 1:10 is more preferable.

The content of the component (A) in the resin composition is preferably 10% by mass or more, more preferably 10% by mass or more, when the resin component is 100% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. Is 20% by mass or more, more preferably 30% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 60% by mass or less, more preferably 55% by mass or less, 50% by mass or less, or 45% by mass or less. is there.

The epoxy equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent 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 is, for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a benzoxazine-based curing agent. , Cyanate ester-based curing agent, carbodiimide-based curing agent and the like. The curing agent may be used alone or in combination of two or more.

As the phenol-based curing agent and the 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 viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395", manufactured by Nippon Steel & Sumitomo Metal Corporation, Examples thereof include "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

The active ester-based curing agent is not particularly limited, but generally contains one molecule of an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. A compound having two or more of them is preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based 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, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, 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 product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM ”,“ EXB-8000L-65TM ”,“ EXB-8150-65T ”(manufactured by DIC),“ EXB9416-70BK ”(manufactured by DIC) as an active ester compound containing a naphthalene structure, and an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, and "DC808" as an active ester-based curing agent which is an acetylated product of phenol novolac. (Made by Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) as active ester-based curing agents that are benzoylated phenol novolacs. And so on.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A disyanate is triazined 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., Ltd.

The amount ratio of the epoxy resin to the curing agent is a ratio of [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent], preferably in the range of 1: 0.01 to 1: 2. 1: 0.05 to 1: 1.5 is more preferable, and 1: 0.1 to 1: 1 is even more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the resin composition layer is further improved.

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

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-based curing agent is preferably 15% by mass or less, more preferably 14% by mass or less, when the resin component is 100% by mass, from the viewpoint of making it easy to adjust the transmission coefficient P within a predetermined range. , More preferably 13% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more.

The content ratio of the active ester-based curing agent to the entire component (B) is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass with respect to 100% by mass of the component (B). % Or more. The upper limit is preferably 75% by mass or less, more preferably 73% by mass or less, and further preferably 70% by mass or less. By containing the active ester-based curing agent so as to be within such a range, it becomes easy to adjust the permeability coefficient P within a predetermined range.

When the resin component is 100% by mass, the content of the component (B) is preferably 20% by mass or less, more preferably 19% by mass or less, and further preferably 18% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 8% by mass or more. By keeping the content of the component (B) within such a range, the adhesion to the substrate can be effectively improved.

-(C) Inorganic filler-
In one embodiment, the resin composition may contain an inorganic filler. The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is preferably 0.35 μm or less, more preferably 0.3 μm or less, still more preferably 0.35 μm or less, from the viewpoint of increasing the surface area of the inorganic filler and adjusting the transmission coefficient P within a predetermined range. It is 0.25 μm or less, 0.2 μm or less, 1.5 μm or less, or 1 μm or less. The lower limit of the average particle size is preferably 0.05 μm or more, more preferably 0.06 μm or more, still more preferably 0.07 μm or more. The upper limit of the average particle size is, for example, "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd. as a commercially available product of an inorganic filler having such an average particle size.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. 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 device, "LA-500" manufactured by HORIBA, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, or the like can be used.

The specific surface area of the inorganic filler is preferably 15 m ² / g or more, more preferably 20 m ² / g or more, still more preferably 25 m ² / g or more, 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 further preferably 40 m ² / g or less. The specific surface area of the inorganic filler can be measured using, for example, a BET fully automatic specific surface area measuring device or the like. More specifically, for the specific surface area, nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and the specific surface area is calculated using the BET multipoint method. Obtained by doing.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler contains a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, and an alkoxysilane. It is preferably treated with one or more surface treatment agents such as a compound, an organosilazane compound, and a titanate-based coupling agent, and particularly preferably treated with an aminosilane coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) and the like.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is such that 100 parts by mass of the component (C) is surface-treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent. It is preferable that the surface is treated with 0.2 parts by mass to 3 parts by mass, and the surface is preferably treated with 0.3 parts by mass to 2 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. preferable.

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 a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

When the resin composition contains the component (C), the content of the inorganic filler is determined when the non-volatile component in the resin composition is 100% by mass from the viewpoint of adjusting the transmission coefficient P within a predetermined range. It is preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably, from the viewpoint of improving the insulation performance and adjusting the balance of the physical properties of the resin composition layer to improve the adhesion to the substrate. It is 60% by mass or less, or 55% by mass or less.

-(D) Thermoplastic resin-
In one embodiment, the resin composition may contain (D) a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples thereof include ether ketone resin and polyester resin, and phenoxy resin is preferable. The thermoplastic resin may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably 38,000 or more, more preferably 40,000 or more, still more preferably 42,000 or more, from the viewpoint of lowering the permeability coefficient P. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K- manufactured by Showa Denko Co., Ltd. as a column. 804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen Examples thereof include a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone) manufactured by Mitsubishi Chemical Corporation. Skeletal-containing phenoxy resin), and also "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30" manufactured by Mitsubishi Chemical Corporation. , "YL6794", "YL7213", "YL7290", "YL7482" and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "electric butyral 4000-2", "electric butyral 5000-A", "electric butyral 6000-C", "electric butyral 6000-EP", and Sekisui manufactured by Denki Kagaku Kogyo Co., Ltd. Examples thereof include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industries.

Specific examples of the polyimide resin include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of the polyamide-imide resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Industries, Ltd.

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.
Specific examples of the polyphenylene ether resin include oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Ltd.

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

Among them, as the thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in a preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins. Among them, as the thermoplastic resin, a phenoxy resin is preferable, 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 permeability coefficient P can be lowered and the surface roughness can be stably formed even if the insulating layer is thin.

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, and further, when the resin component is 100% by mass. It is preferably 1% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less. By setting the content of the component (D) within such a range, the permeability coefficient P can be lowered and the surface roughness can be stably formed even if the insulating layer is thin.

-(E) Curing accelerator-
In one embodiment, the resin composition may contain (E) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing 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 alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium 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) phenol, and 1,8-diazabicyclo. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 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 , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. 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 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

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

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, and further, when the resin component is 100% by mass. It is preferably 0.1% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. By setting the content of the curing accelerator within such a range, it becomes easy to improve the adhesion to the substrate.

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

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is hard to hydrolyze is preferable, 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, preferably 0.5% by mass, assuming that the non-volatile component in the resin composition is 100% by mass. ~ 15% by mass is more preferable, and 0.5% by mass to 10% by mass is further preferable.

-(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 when forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

As the rubber particles, commercially available products may be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, preferably 0.2% by mass, assuming that the non-volatile component in the resin composition is 100% by mass. By mass% to 10% by mass is more preferable, and 0.3% by mass to 5% by mass, or 0.5% by mass to 3% by mass is further preferable.

-(H) Any additive-
In one embodiment, the resin composition may further contain other additives, if necessary, and such other additives include, for example, an organic copper compound, an organic zinc compound, an organic cobalt compound and the like. Examples thereof include organometallic compounds of the above, thickeners, defoaming agents, leveling agents, adhesion-imparting agents, resin additives such as colorants, and the like.

<Physical characteristics and applications of the resin composition layer>
The permeation coefficient P of the cured product obtained by thermally curing the resin composition layer at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes makes it easy to improve the balance of the physical properties of the resin composition and improves the adhesion to the substrate. 1.2 cc / m ² · mm ^-1 · day · atom or more, preferably 1.5 cc / m ² · mm ^-1 · day · atom or more, more preferably ² cc / m 2 · mm ^{− It is 1}・ day ・ atom or more. The upper limit of the permeation coefficient P is 5 cc / from the viewpoint of making it difficult for oxygen to permeate into the insulating layer, and as a result, oxidizing the metal such as copper foil which is the base of the insulating layer is suppressed and improving the base adhesion. It is m ² · mm ^-1 · day · atom or less, preferably 4.5 cc / m ² · mm ^-1 · day · atom or less, more preferably 4 cc / m ² · mm ^-1 · day · atom or less. .. The permeability coefficient P can be set within such a range by adjusting the contents of the curing agent, the inorganic filler, the thermoplastic resin, and the like, for example. The permeability coefficient P can be measured according to the description of <Measurement of oxygen permeability and permeability coefficient> described later.

The oxygen permeability of the cured product obtained by thermosetting the resin composition layer at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is the physical characteristics of the resin composition when measured assuming that the thickness of the cured product is 60 μm. From the viewpoint of easily improving the balance and thereby improving the adhesion to the substrate, it is preferably 20 cc / m ² · day · atm or more, more preferably 25 cc / m ² · day · atom or more, and further preferably 30 cc / m ^2.・ It is day ・ atom or more. The upper limit of the oxygen transmittance is preferably 80 cc from the viewpoint of making it difficult for oxygen to permeate into the insulating layer, and as a result, oxidizing the metal such as copper foil which is the base of the insulating layer is suppressed and improving the adhesion to the base. / M ² · day · Atom or less, more preferably 75 cc / m ² · day · atom or less, still more preferably 70 cc / m ² · day · atom or less. The oxygen permeability can be measured according to the description of <Measurement of oxygen permeability and permeability coefficient> described later.

The cured product obtained by thermally curing the resin composition layer at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes has a permeability coefficient P of 1.2 cc / m ² · mm ^-1 · day · atom or more 5 cc /. Since it is m ² · mm ^-1 · day · atom or less, it exhibits a characteristic of being excellent in peeling strength (adhesion to the base) from the copper foil. That is, it provides an insulating layer having excellent adhesion to the substrate. The substrate adhesion is the load required to peel off a small piece having a width of 10 mm, and is preferably 0.2 kgf or more, more preferably 0.25 kgf or more, and further preferably 0.3 kgf or more. The upper limit may be preferably 1 kgf or less, 10 kgf or less, or the like. The base adhesion can be measured according to the description of <Measurement of base adhesion> described later.

The cured product obtained by thermally curing the resin composition layer at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes exhibits a characteristic of excellent reflow resistance. That is, it provides an insulating layer having excellent reflow resistance. Even if the insulating layer formed by using the resin composition layer is subjected to the reflow step of reproducing the reflow temperature of the peak temperature of 260 ° C. 20 times or more, the peeling between the insulating layer and the conductor layer is preferably 2 or less. It is more preferable that there is no peeling between the insulating layer and the conductor layer. The reflow resistance can be evaluated according to the method described in <Evaluation of reflow resistance> described later.

The resin composition layer of the present invention provides an insulating layer (cured product of the resin composition layer) having excellent substrate adhesion and reflow resistance even if the thickness is as thin as 15 μm or less. Therefore, the resin composition layer of the present invention can be suitably used as a resin composition for forming an insulating layer contained in an electronic component, and for example, for forming wiring by a semi-additive method (semi-additive method). It can be suitably used as a resin composition (for forming wiring by). Further, 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 interlayer insulation of the printed wiring board can be used. It can be more preferably used as a resin composition layer for forming a layer (resin composition layer for an interlayer insulating layer of a printed wiring board).
Further, 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 encapsulating an electronic member can also be preferably used, and for example, as a resin composition for encapsulating a semiconductor chip (resin composition for forming a sealing layer of a semiconductor chip). It can be preferably used.

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

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. Of these, 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, aluminum foil, and the like, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples include "AL-5" and "AL-7", "Lumilar T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further include other layers, if desired. Examples of such other layers include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust and the like to the surface of the resin composition layer and scratches.

For the resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

The resin sheet can be rolled up 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) an epoxy resin and (B) a resin composition containing a curing agent, has a thickness of 15 μm or less, and is obtained by thermosetting at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes. The cured product of the resin composition layer having a permeation coefficient P of 1.2 cc / m ² · mm ^-1 · day · atom or more and 5 cc / m ² · mm ^-1 · day · atom or less. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer and the second conductor layer (the conductor layer is a wiring layer). is there).
In a preferred embodiment, the insulating layer is formed of 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 μm or less, more preferably 5.5 μm or less, still more preferably 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown by an example in FIG. It refers to the thickness t1 of the insulating layer 3 between the main surface 21 of the 11 and the second conductor layer 2. The first and second conductor layers are adjacent conductor layers via an insulating layer, and the main surface 11 and the main surface 21 face each other.

The thickness t2 of the entire insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and further preferably 10 μm or less. The lower limit is not particularly limited, but is usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

The printed wiring board can be manufactured by a method including the following steps (I) and (II) using the above-mentioned resin sheet.
(I) A step of laminating the resin composition layer of the resin sheet on the inner layer substrate so as to be bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer.

The "inner layer substrate" used in the step (I) is a member that becomes a substrate of a printed wiring board, and is, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. And so on. Further, 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 in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Further, an intermediate product in which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

After the lamination, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

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

The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably 170 ° C. to 170 ° C. The curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

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

In manufacturing the printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the support is removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

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

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with an oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

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, still more preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more, and the like. The 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, and further preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more, and the like. The arithmetic mean roughness (Ra) and the 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. When the conductor layer is not formed on the inner layer substrate, the step (V) is a step of forming the first conductor layer, and when the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. The step (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 is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed of a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable. A metal layer is more preferred.

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

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the desired printed wiring board design.

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

Since the resin sheet of the present invention provides an insulating layer having good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board. The component-embedded circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured by using the resin sheet of the present invention has an embodiment including an insulating layer which is a cured product of the resin composition layer of the resin sheet and an embedded wiring layer embedded in the insulating layer. May be good.

[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 semiconductor devices include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The mounting method of the semiconductor chip in manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer. Examples thereof include a mounting method using (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 build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco Ltd.), and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction type particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation), the particle size distribution was measured by a batch cell method, and the average particle size based on the median diameter was calculated.

<Measurement of specific surface area of inorganic filler>
Using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech), nitrogen gas is adsorbed on the sample surface, and the specific surface area is calculated using the BET multipoint method to calculate the specific surface area of the inorganic filler. Was measured.

<Inorganic filler used>
Inorganic filler 1: N-phenyl-3-aminopropyltri for 100 parts of spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078 μm, specific surface area 30.7 m ^{2 / g).} Surface-treated with 2 parts of methoxysilane (KBM573, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
Inorganic filler 2: N-phenyl-3-aminopropyltrimethoxysilane (N-phenyl-3-aminopropyltrimethoxysilane) per 100 parts of spherical silica (“SC2500SQ” manufactured by Admatex, average particle size 0.77 μm, specific surface area 11.2 m ^{2 / g).} KBM573) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Surface-treated with 1 part.

<Preparation of resin composition 1>
6 parts of bixilenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Co., Ltd. "ZX1658GS", epoxy equivalent about 135) 2 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid content Two parts of 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution, 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, there, 4 parts of a cresol novolac-based curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC, a hydroxyl group equivalent of about 151, a 2-methoxypropanol solution having a solid content of 50%), and activity. 6 parts of ester-based curing agent ("EXB-8150-65T" manufactured by DIC, active group equivalent of about 229, toluene solution of 65% by mass of non-volatile component), 50 parts of inorganic filler 1, amine-based curing accelerator (4- 0.05 parts of dimethylaminopyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 1.

<Preparation of resin composition 2>
6 parts of bixilenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 15 parts, bisphenol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ZX1059", epoxy equivalent about 169, bisphenol A type and bisphenol F type 1: 1 mixture) 4 2 parts, naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC, epoxy equivalent about 213), 2 parts, phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone with a solid content of 30% by mass: methyl ethyl ketone (MEK) ) 1: 1 solution, Mw = 44000) 2 parts 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, there, 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity. Ester-based curing agent ("EXB-8000L-65M" manufactured by DIC, active group equivalent of about 220, MEK solution of 65% by mass of non-volatile component) 6 parts, inorganic filler 1 40 parts, amine-based curing accelerator (4- 0.05 parts of dimethylaminopyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 2.

<Preparation of resin composition 3>
6 parts of bixilenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 15 parts, bisphenol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ZX1059", epoxy equivalent about 169, bisphenol A type and bisphenol F type 1: 1 mixture) 4 2 parts, naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC, epoxy equivalent about 213), 2 parts, phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone with a solid content of 30% by mass: methyl ethyl ketone (MEK) ) 1: 1 solution, Mw = 44000) 2 parts 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, there, 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity. Ester-based curing agent ("EXB-8000L-65M" manufactured by DIC, active group equivalent of about 220, MEK solution of 65% by mass of non-volatile component) 12 parts, inorganic filler 1 40 parts, amine-based curing accelerator (4- 0.05 parts of dimethylaminopyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKICHNO) to prepare a resin composition 3.

<Preparation of resin composition 4>
6 parts of bixilenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Co., Ltd. "ZX1658GS", epoxy equivalent about 135) 2 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid content Two parts of 30% by mass of cyclohexanone: a 1: 1 solution of methyl ethyl ketone (MEK)) 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, there, 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity. Ester-based curing agent ("EXB-8000L-65M" manufactured by DIC, active group equivalent of about 220, MEK solution of 65% by mass of non-volatile component) 6 parts, inorganic filler 2 160 parts, amine-based curing accelerator (4- 0.05 parts of dimethylaminopyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKICHNO) to prepare a resin composition 4.

The components used in the preparation of the resin compositions 1 to 4 and their blending amounts (mass parts of non-volatile components) are shown in the table below. The abbreviations in the table below are as follows.
YX4000HK: Bixylenol type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 185
ESN475V: Naphthalene type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 332
YL7760: Bisphenol AF type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 238
EXA-7311-G4: Naftylene ether type epoxy resin, manufactured by DIC Corporation, epoxy equivalent about 213
ZX1059: Bisphenol type epoxy resin, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent about 169, 1: 1 mixture of bisphenol A type and bisphenol F type ZX1658GS: Cyclohexane type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 135
LA-3018-50P: Triazine skeleton-containing cresol novolac-based curing agent, manufactured by DIC, 2-methoxypropanol solution with hydroxyl equivalent of about 151 and solid content of 50% EXB-8000L-65M: active ester-based curing agent, manufactured by DIC, MEK solution EXB-8150-65T with an active group equivalent of about 220 and a non-volatile component of 65% by mass: Active ester-based curing agent, manufactured by DIC, active group equivalent of about 229, toluene solution of a non-volatile component of 65% by mass YX7553BH30: Phenoxy resin, Mitsubishi A 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) with a solid content of 30% by mass, manufactured by Kagakusha, Mw = 35000
YX7500BH30: Phenoxy resin, manufactured by Mitsubishi Chemical Corporation, cyclohexanone with a solid content of 30% by mass: 1: 1 solution of methyl ethyl ketone (MEK), Mw = 44000
DMAP: Content of amine-based curing accelerator and 4-dimethylaminopyridine curing agent: Content of curing agent when the resin component in the resin composition is 100% by mass Content of active ester-based curing agent: Resin composition Content of active ester-based curing agent when the resin component in the product is 100% by mass Content of the inorganic filler: Content of the inorganic filler when the non-volatile component in the resin composition is 100% by mass

<Making a resin sheet>
As a support, a PET film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., "Release PET") treated with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). I prepared.

Each resin composition is uniformly applied on a mold release PET with a die coater so that the thickness of the resin composition layer after drying is 10 μm, and dried at 70 ° C. to 95 ° C. for 2 minutes to release the mold. A resin composition layer was obtained on PET. Next, a rough surface of a polypropylene film (“Alfan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is bonded to the resin composition layer on the surface that is not bonded to the support of the resin sheet. Laminated in. As a result, a resin sheet A composed of a release PET (support), a resin composition layer, and a protective film was obtained.
Further, a resin sheet B was obtained in the same manner as the resin sheet A except that each resin composition was uniformly applied with a die coater so that the thickness of the resin composition layer after drying was 30 μm.

<Measurement of thickness of resin composition layer, etc.>
The thickness was measured using a contact type film thickness meter (Mitutoyo Co., Ltd., MCD-25MJ).

<Evaluation of reflow resistance>
-Preparation of evaluation substrate A-
(1) Copper-clad laminate As a copper-clad laminate, a glass cloth base material with copper foil layers laminated on both sides Epoxy resin double-sided copper-clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company, Inc. "HL832NSF LCA" manufactured by 255 x 340 mm size) was prepared.

(2) Laminating of resin sheets The protective film is peeled off from each resin sheet A produced in Examples and Comparative Examples, and a batch type vacuum pressurizing laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700) is used. , The resin composition layer was laminated on both sides of the copper-clad laminate so as to be in contact with the copper-clad laminate. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, heat pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of Resin Composition Layer The copper-clad laminate on which the resin sheet is laminated is heat-cured for 30 minutes after being placed in an oven at 100 ° C. and then transferred to an oven at 180 ° C. for 30 minutes for insulation. A layer was formed and the release PET was peeled off. This is referred to as a cured substrate A.

(4) Step of Roughening 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:
In a swollen solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 10 minutes, then an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP"" , Aqueous solution with potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, and finally in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", sulfuric acid aqueous solution). After soaking at 40 ° C. for 5 minutes, it was dried at 80 ° C. for 15 minutes. This is referred to as a roughened substrate A.

(5) Step of forming a conductor layer (5-1) Electroplating-free plating step In order to form a conductor layer on the surface of the insulating layer of the roughened substrate A, a plating step including the following steps 1 to 6 (manufactured by Atotech Japan Co., Ltd.) A conductor layer was formed by performing a copper plating step) using a chemical solution.

1. 1. Alkaline cleaning (cleaning of the surface of the insulating layer with via holes and charge adjustment)
The surface of the roughened substrate A was washed with a cleaning cleaner security 902 (trade name) at 60 ° C. for 5 minutes.
2. Soft etching (cleaning inside the via hole)
The surface of the roughened substrate A was treated with an aqueous solution of sodium sulfate-acidic peroxodisulfate at 30 ° C. for 1 minute.
3. 3. Predip (Adjustment of charge on the surface of the insulating layer for Pd application)
The surface of the roughened substrate A was prepared by Pre. Treatment was performed at room temperature for 1 minute using Dip Neoganth B (trade name).
4. Add activator (give Pd to the surface of the insulating layer)
The surface of the roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35 ° C. for 5 minutes.
5. Reduction (Reduction of Pd applied to the insulating layer)
The surface of the roughened substrate A was subjected to Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. Using a mixed solution with (trade name), the treatment was carried out at 30 ° C. for 5 minutes.
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
The surface of the roughened substrate A is mixed with Basic Solution Printtganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name). The solution was treated at 35 ° C. for 15 minutes. The thickness of the formed electroless copper plating layer was 1 μm.

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

-Evaluation of reflow resistance-
The evaluation substrate A was cut into 100 mm × 100 mm test pieces. For the obtained test piece, IPC / JEDEC J-STD-020C ("Moisture / Reflecticity Classification For Non-Hermetic Solid State Surface 7 Month" Surface Mount 7 month) using a reflow device ("HAS6116" manufactured by Antom) The simulated reflow process was repeated 20 times with the described reflow temperature profile (lead-free assembly profile; peak temperature 260 ° C.). Then, the reflow resistance was evaluated according to the following evaluation criteria.
Evaluation criteria:
◯: 2 or less peeling between the insulating layer and the conductor ×: 3 or more peeling between the insulating layer and the conductor

<Measurement of substrate adhesion>
(1) Base treatment of copper foil The glossy surface of "3EC-III" (electric field copper foil, 35 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. is immersed in MEC etch bond "CZ-8101" manufactured by MEC to roughen the copper surface. (Ra value = 1 μm) was performed, and a rust preventive treatment (CL8300) was applied. This copper foil is called CZ copper foil. Further, it was heat-treated in an oven at 130 ° C. for 30 minutes.

(2) Lamination of Copper Foil and Formation of Insulation Layer The protective film is peeled off from each resin sheet A produced in Examples and Comparative Examples, and a batch type vacuum pressurizing laminator (“MVLP-500” manufactured by Meiki Co., Ltd.) is used. Both sides of the inner layer circuit board were laminated so that the resin composition layer was bonded to the inner layer circuit board. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. After laminating, the release PET, which is a support, was peeled off. The treated surface of the CZ copper foil of "3EC-III" was laminated on the resin composition layer from which the support was peeled off under the same conditions as described above. Then, a sample was prepared by curing the resin composition layer at 190 ° C. for 90 minutes to form an insulating layer.

(3) Measurement of Copper Foil Peeling Strength (Adhesion to Base) The prepared sample was cut into small pieces of 150 × 30 mm. Use a cutter to make a notch in the copper foil part of a small piece with a width of 10 mm and a length of 100 mm, peel off one end of the copper foil, and use a gripper (manufactured by JIS, Autocom type testing machine, " AC-50C-SL "), and using an Instron universal tester, measure the load when 35 mm is peeled off vertically at a speed of 50 mm / min at room temperature in accordance with JIS C6481. , Evaluated according to the following criteria.
Evaluation Criteria ○: Measurement result of substrate adhesion is 0.2 kgf or more ×: Measurement result of substrate adhesion is less than 0.2 kgf

<Measurement of oxygen permeability and permeability coefficient>
-Preparation of cured sheet-
The protective film is peeled off from each of the resin sheets B produced in Examples and Comparative Examples, and the resin composition layers are brought into contact with each other using a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials, CVP700). As described above, two resin sheets B were laminated. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, the release PET on one surface was peeled off, the resin composition layer was cured under the curing conditions of 90 ° C. for 90 minutes, and then the release PET on the other surface was peeled off to prepare a cured sheet B.

-Measurement of oxygen permeability and permeability coefficient-
Cured in an atmosphere of 23 ° C. and 0% RH and in an atmosphere of 23 ° C. and 90% RH according to JIS-K7126 (isopressure method) using an oxygen permeability measuring device (OX-TRAN2 / 21 manufactured by MOCON). The oxygen permeability of Sheet B was measured. Note that RH represents relative humidity. Further, the permeability coefficient P (oxygen permeability coefficient P) was calculated by dividing by the thickness based on the oxygen permeability of the cured sheet B.
Where permeability coefficient P is not more than ^{5.0cc / m 2 · mm -1 ·} day · atom "○", the case where transmission coefficient P is more than ^{5.0cc / m 2 · mm -1 ·} day · atom " × ”was evaluated. Further, when the transmission coefficient P is 1.2 cc / m ² · mm ^-1 · day · atom or more, it is “◯”, and the transmission coefficient P is ^{less than 1.2 cc / m 2} · mm ^-1 · day · atom. The case was evaluated as "x".

In Examples 1 and 2, it has been confirmed that even when the components (C) to (E) are not contained, the same result as in the above-mentioned Examples is obtained, although the degree is different.

1 First conductor layer 11 Main surface of the first conductor layer 2 Second conductor layer 21 Main surface of the second conductor layer 3 Insulation layer t1 Spacing between the first conductor layer and the second conductor layer (first And the thickness of the insulating layer between the second conductor layers)
t2 Thickness of the entire insulating layer

Claims (16)

A resin composition layer containing (A) an epoxy resin and (B) a resin composition containing a curing agent.
The thickness of the resin composition layer is 15 μm or less,
The oxygen permeability coefficient P of the cured product obtained by thermosetting the resin composition layer at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is 1.2 cc / m ² · mm ^-1 · day · atom or more 5 cc. / M ² · mm ^-1 · day · atom or less, resin composition layer. The resin composition layer according to claim 1, which is used for forming wiring by a semi-additive method. (C) The resin composition layer according to claim 1 or 2, which contains 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 non-volatile component in the resin composition is 100% by mass. The resin composition layer according to claim 3 or 4, wherein the average particle size of the component (C) is 0.05 μm or more and 0.35 μm or less. The resin composition layer according to any one of claims 1 to 5, wherein the content of the component (B) is 20% by mass or less when the resin component is 100% by mass. The resin composition layer according to any one of claims 1 to 6, 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-based curing agent is 15% by mass or less when the resin component is 100% by mass. (D) The resin composition layer according to any one of claims 1 to 8, which contains a thermoplastic resin. The resin composition layer according to claim 9, wherein the component (D) has a weight average molecular weight of 38,000 or more. Oxygen permeability coefficient P ^is not more than ^{2cc / m 2 · mm -1 ·} day · atom or ^{4cc / m 2 · mm -1 ·} day · atom, the resin composition according to any one of claims 1 to 10 Material layer. The resin composition layer according to any one of claims 1 to 11, which is used for forming an insulating layer of a printed wiring board. The resin composition layer according to any one of claims 1 to 12, which is used for forming an interlayer insulating layer of a printed wiring board. A resin sheet comprising a support and a resin composition layer according to any one of claims 1 to 13 provided on the support. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer.
A printed wiring board, 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 including the printed wiring board according to claim 15.

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