JP2019073603A - Resin composition layer - Google Patents

Abstract

To provide a resin composition layer capable of suppressing a haloing phenomenon even when a thickness is thin.SOLUTION: A resin composition layer contains a resin composition and has a thickness of 15 μm or less, where the resin composition contains (A) an epoxy resin, (B) a curing agent, (C) magnesium hydroxide and (D) silica.SELECTED DRAWING: Figure 1

Description

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

  In recent years, in order to achieve miniaturization of electronic devices, further thinning of printed wiring boards has been promoted. Along with this, miniaturization of wiring circuits in the inner layer substrate has been advanced. For example, Patent Document 1 describes a resin sheet (adhesive film) capable of coping with a low dielectric loss tangent, which includes a support and a resin composition layer.

JP, 2014-5464, A

  The present inventors examined thinning of the resin composition layer of the resin sheet in order to achieve further miniaturization and thinning of electronic devices. As a result of examination, the present inventors have found that when a thin resin composition layer is applied to an insulating layer, when a via hole is formed in the insulating layer, a haloing phenomenon occurs. Here, the haloing phenomenon refers to a phenomenon in which the resin of the insulating layer is discolored around the via hole. Such haloing phenomenon usually occurs when the resin around the via hole is deteriorated when the via hole is formed.

  The above-mentioned problems are caused only by thinning the thickness of the resin composition layer, and are new problems which have not been known conventionally. From the viewpoint of enhancing the conduction reliability between the layers of the printed wiring board, these problems are desired to be solved.

  The present invention has been made in view of the above problems, and a resin composition layer capable of suppressing the haloing phenomenon even if the thickness is thin; a resin sheet containing the resin composition layer described above; which can suppress the haloing phenomenon It is an object of the present invention to provide a printed wiring board including a thin insulating layer; and a semiconductor device including the above printed wiring board.

As a result of intensive studies to solve the above-mentioned problems, the present inventors found that (A) an epoxy resin, (B) a curing agent, (C) magnesium hydroxide, and (D) a resin composition containing a combination of silica The inventors have found that the above problems can be solved, and completed the present invention.
That is, the present invention includes the following contents.

[1] A resin composition layer containing a resin composition and having a thickness of 15 μm or less,
A resin composition layer, wherein the resin composition comprises (A) epoxy resin, (B) curing agent, (C) magnesium hydroxide, and (D) silica.
[2] The resin composition layer according to [1], wherein the average particle size of the component (D) is 3 μm or less.
[3] The resin composition layer according to [1] or [2], wherein the average particle diameter of the component (D) is 0.3 μm or less.
[4] According to any one of [1] to [3], wherein the content of the component (D) is 3% by mass or more and 50% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Resin composition layer.
[5] Any one of [1] to [4], wherein the component (B) is one or more selected from a phenol type curing agent, an active ester type curing agent, a cyanate ester type curing agent, and a benzoxazine type curing agent The resin composition layer according to claim 1.
[6] According to any one of [1] to [5], wherein the content of the component (A) is 3% by mass or more and 50% by mass or less, when the nonvolatile component in the resin composition is 100% by mass. Resin composition layer.
[7] The resin composition layer according to any one of [1] to [6], wherein the component (C) is surface-treated with a surface treatment agent.
[8] The resin composition layer according to [7], wherein the surface treatment agent is an alkoxysilane compound.
[9] The resin composition layer according to [8], wherein the alkoxysilane compound has an amino group or a vinyl group.
[10] The resin composition layer according to any one of [7] to [9], wherein the amount of the surface treatment agent is 5 parts by mass or less with respect to 100 parts by mass of magnesium hydroxide.
[11] According to any one of [1] to [10], wherein the content of the component (C) is 2% by mass or more and 40% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Resin composition layer.
[12] The resin composition layer according to any one of [1] to [11], which is a resin composition layer for an insulating layer of a multilayer printed wiring board.
[13] The resin composition layer according to any one of [1] to [12], which is for forming an insulating layer having a via hole with a top diameter of 35 μm or less.
[14] A resin sheet comprising a support and a resin composition layer according to any one of [1] to [13] provided on the support.
[15] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition layer according to any one of [1] to [13].
[16] A semiconductor device comprising the printed wiring board according to [15].

  According to the present invention, a resin composition layer capable of suppressing the haloing phenomenon even when the thickness is thin; a resin sheet containing the above resin composition layer; a printed wiring board including a thin insulating layer capable of suppressing the haloing phenomenon; And a semiconductor device including the above printed wiring board.

FIG. 1 is a cross-sectional view schematically showing an insulating layer obtained by curing a resin composition layer according to the first embodiment of the present invention, together with an inner layer substrate. FIG. 2: is a top view which shows typically the surface on the opposite side to a conductor layer of the insulating layer obtained by hardening the resin composition layer which concerns on 1st embodiment of this invention. FIG. 3 is a cross-sectional view schematically showing an insulating layer after roughening treatment obtained by curing the resin composition layer according to the first embodiment of the present invention, along with the inner layer substrate. FIG. 4 is a schematic cross-sectional view of a printed wiring board according to a second embodiment of the present invention.

  Hereinafter, the present invention will be described in detail by way of embodiments and exemplifications. However, the present invention is not limited to the embodiments and exemplifications listed below, and can be implemented with arbitrary modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

  In the following description, the “resin component” of the resin composition refers to the components excluding the (C) component and the (D) component among the non-volatile components contained in the resin composition.

[Resin composition layer]
The resin composition layer of the present invention is a thin resin composition layer having a thickness equal to or less than a predetermined value. Moreover, the resin composition which the resin composition layer of this invention contains (A) epoxy resin, (B) hardening | curing agent, (C) magnesium hydroxide, and (D) silica.

  By using such a resin composition layer, a thin insulating layer having a predetermined value or less can be obtained. And the desired effect of the present invention that the haloing phenomenon at the time of carrying out roughening processing to the insulating layer in which the via hole was formed can be controlled can be acquired.

  The resin composition may further contain (E) a thermoplastic resin, (F) a curing accelerator, and (G) optional additives, as needed. Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(A) Epoxy resin>
Examples of the epoxy resin as the component (A) include bixylenol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, Tris phenol type epoxy resin, naphthol 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, glycidyl amine type epoxy resin, glycidyl ester Type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic Epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. . The epoxy resin may be used alone or in combination of two or more.

  The resin composition preferably contains, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining the desired effects of the present invention remarkably, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50 mass with respect to 100 mass% of the non-volatile component of the (A) epoxy resin. % Or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

  The epoxy resin includes an epoxy resin which is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin which is solid at a temperature of 20 ° C. (which may be referred to as “solid epoxy resin”). There is. The resin composition may contain only the liquid epoxy resin as the epoxy resin (A), or may contain only the solid epoxy resin, but the liquid epoxy resin and the solid epoxy resin should be contained in combination. Is preferred. (A) By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, the flexibility of the resin composition layer can be improved, or the breaking strength of the cured product of the resin composition layer can be improved. it can.

  The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

  As liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, ester skeleton The alicyclic epoxy resin which has, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, and the epoxy resin which has a butadiene structure are preferable, and a cyclohexane type epoxy resin is more preferable.

  Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “jER828EL”, “825”, “epicoat” manufactured by Mitsubishi Chemical Corporation. 828 EL "(bisphenol A type epoxy resin);" jER 807 "and" 1750 "(bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corp .;" jER 152 "(phenol novolac epoxy resin) manufactured by Mitsubishi Chemical Corp .; manufactured by Mitsubishi Chemical Corp. "630", "630LSD" (glycidyl amine type epoxy resin); "ZX1059" (a mixture of bisphenol A epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; EX made by Nagase ChemteX −721 ”(glycidyl Stel type epoxy resin); "Ceroxide 2021 P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel; manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Examples include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin). These may be used alone or in combination of two or more.

  The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

  As solid epoxy resin, bixylenol 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, biphenyl Type epoxy resin, naphthalene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin is preferable, and bixylenol type epoxy resin, naphthalene type epoxy resin, and bisphenol More preferred is an AF type epoxy resin.

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” manufactured by DIC, “HP-4710” (naphthalene type tetrafunctional epoxy resin); “N-690” (cresol novolac epoxy resin); “N-695” (cresol novolac epoxy resin) manufactured by DIC; “HP-7200” (dicyclopentadiene type epoxy resin) manufactured by DIC; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” manufactured by DIC Corporation Naphthylene ether type epoxy resin); “EPPN-502H” (Trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin); “NC7000L” (naphthol novolac epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; Chemical made "ESN 475 V" (naphthalene type epoxy resin); Nippon Steel & Sumikin Chemical make "ESN 485" (naphthol novolac type epoxy resin); Mitsubishi Chemical company made "YX4000H", "YX 4000", "YL 6121" (biphenyl type Epoxy resin); “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. “YX 8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; “PG-100” manufactured by Osaka Gas Chemical Co., Ltd., “CG- 500 "; YL manufactured by Mitsubishi Chemical Corporation 760 "(bisphenol AF type epoxy resin);" YL 7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corp .;" jER 1010 "manufactured by Mitsubishi Chemical Corp. (solid bisphenol A type epoxy resin);" jER 1031S manufactured by Mitsubishi Chemical Corp. " (Tetraphenylethane type epoxy resin) etc. are mentioned. These may be used alone or in combination of two or more.

  (A) When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, their quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1:40 by mass ratio. More preferably, it is 1: 3 to 1:30, and particularly preferably 1: 5 to 1:20. When the ratio of the liquid epoxy resin to the solid epoxy resin is in such a range, the desired effect of the present invention can be remarkably obtained. Furthermore, usually, when used in the form of a resin sheet, adequate tackiness is provided. In addition, usually, when used in the form of a resin sheet, sufficient flexibility is obtained, and the handleability is improved. Furthermore, usually, a cured product having sufficient breaking strength can be obtained.

  The epoxy equivalent of the (A) epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and still more preferably 110 to 1000. By being in this range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with a small surface roughness can be provided. Epoxy equivalent is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin (A) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500, from the viewpoint of obtaining the desired effects of the present invention remarkably.
The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

  The amount of the (A) epoxy resin in the resin composition is preferably 3%, based on 100% by mass of the non-volatile component in the resin composition, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. % Or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 30% by mass or more. The upper limit of the content of the epoxy resin is preferably 50% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less from the viewpoint of obtaining the desired effects of the present invention remarkably.

<(B) Hardening agent>
The resin composition contains a curing agent as component (B). The curing agent (B) usually has a function of reacting with the (A) epoxy resin to cure the resin composition.

  As the curing agent (B), those having an effect of curing the epoxy resin (A) can be used. Examples of the curing agent (B) include active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. The curing agents may be used alone or in combination of two or more.

  As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as an active ester curing agent, two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. in one molecule The compound which it has is preferable. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester-based curing agents obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester-based curing agents obtained from carboxylic acid compounds and phenol compounds and / or naphthol compounds are more preferable. .

  Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid.

  As a phenol compound or naphthol compound, for example, hydroquinone, resorcine, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac and the like can be mentioned. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol with one molecule of dicyclopentadiene.

  Preferred specific examples of the active ester-based curing agent include 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 compound of phenol novolac, and a benzoyl compound of phenol novolac And active ester compounds. Among them, 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 bivalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

  Commercial products of the active ester-based curing agent 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);" EXB 9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure; containing acetylated phenol novolak "DC 808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound; "YLH 1026" (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated phenol novolak; active ester curing agent which is an acetylated phenol novolak “DC 808” (Mitsubishi Chemical Co., Ltd.); “YLH1026” (Mitsubishi Chemical Co., Ltd.), “YLH 1030” (Mitsubishi Chemical Co., Ltd.), “YLH 1048” (Mitsubishi Chemical Co., Ltd.) And the like.

  From the viewpoint of heat resistance and water resistance, those having a novolac structure are preferable as the phenol-based curing agent and the naphthol-based curing agent. 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 naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd .; “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”; “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, manufactured by Nippon Steel Sumikin Chemical Co., Ltd .; manufactured by DIC Corporation “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500”, and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Highpolymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  As a cyanate ester-based curing agent, for example, bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylene bis (2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluoro bisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1, 1-bis (4- cyanate phenyl methane), bis (4- cyanate 3,5- dimethyl) A bifunctional cyanate resin such as phenyl) methane, 1,3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) thioether, and bis (4-cyanatophenyl) ether; Phenolic novolak and Polyfunctional cyanate resin derived from resol novolac; prepolymer these cyanate resin is partially triazine of; and the like. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolac-type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA230" manufactured by Lonza Japan Co., Ltd. And “BA 230 S 75” (a prepolymer in which part or all of bisphenol A dicyanate is triazinated to form a trimer), and the like.

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

  The amount of the (B) curing agent in the resin composition is preferably 5% by mass or more, more preferably 100% by mass of the resin component in the resin composition, from the viewpoint of obtaining the desired effects of the present invention remarkably. It is 8% by mass or more, more preferably 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

  Among the above-mentioned, as the (B) curing agent, from the viewpoint of obtaining the desired effects of the present invention remarkably, it is selected from phenolic curing agents, active ester curing agents, cyanate ester curing agents, benzoxazine curing agents. It is preferable that it is 1 or more types, and it is more preferable that it is an active ester type curing agent.

  When the curing agent (B) contains an active ester-based curing agent, the content of the active ester-based curing agent is preferably 3% by mass or more, more preferably 100% by mass of the resin component in the resin composition. It is 5% by mass or more, more preferably 8% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

  When the epoxy group number of the (A) epoxy resin is 1, the active group number of the (B) curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.24 or more, and preferably Is 2 or less, more preferably 1.5 or less, still more preferably 1 or less, and particularly preferably 0.5 or less. Here, “the number of epoxy groups of (A) epoxy resin” is a value obtained by totaling all values obtained by dividing the mass of the nonvolatile component of (A) epoxy resin present in the resin composition by the epoxy equivalent. Moreover, "the active group number of (B) hardening | curing agent" is the value which totaled all the values which remove | divided the mass of the non-volatile component of the (B) hardening | curing agent which exists in a resin composition by active group equivalent. When the number of active groups of (A) epoxy resin is 1 and the number of active groups of (B) curing agent is in the above range, the desired effect of the present invention can be remarkably obtained, and usually, the resin composition The heat resistance of the cured product of the product layer is further improved.

<(C) Magnesium hydroxide>
The resin composition contains magnesium hydroxide as the component (C). By including the component (C) in the resin composition, an insulating layer capable of suppressing the haloing phenomenon can be obtained, and furthermore, the flame retardancy of the cured product of the resin composition layer can be improved.

  The magnesium hydroxide used as the component (C) may be either a synthetic product or a natural product. As the component (C), one type may be used alone, or two or more types may be used in combination.

  Examples of commercially available products of magnesium hydroxide include “EP-4A”, “EP-2E”, “EP-2A”, and “EP-1SII” manufactured by Kamijima Chemical Industries, Ltd., and “Echo Mug Z- manufactured by Tateho Chemical Industries, Ltd. 10 "," Echo Mug PZ-1 "," MGZ-1 "made by Sakai Chemical Industry Co., Ltd.," MGZ-3 "," Kisuma 5E "made by Kyowa Chemical Industry Co., Ltd.," Kisuma 8 SN "," Kisuma 5A "," Kisuma 5L and the like.

  Magnesium hydroxide is usually contained in the resin composition in the form of particles. The average particle diameter of magnesium hydroxide is preferably 0.5 μm or more, more preferably 0.8 μm or more, still more preferably 1 μm or more, preferably 3 μm or less, from the viewpoint of effectively suppressing the haloing phenomenon. Preferably it is 2 micrometers or less, More preferably, it is 1.5 micrometers or less.

  The shape of magnesium hydroxide is not particularly limited as long as it is particulate, but it may be elliptical (flaky) from the viewpoint of effectively suppressing the haloing phenomenon. In this case, the aspect ratio is preferably 1 or more, more preferably 1.2 or more, further preferably 1.4 or more, preferably 10 or less, more preferably 9 or less, still more preferably 8 or less. The aspect ratio means the value obtained by dividing the length of the major axis of the particle (the length of the longest part of the particle diameter) by the length of the minor axis (the length in the vertical direction of the major axis).

  The average particle size of magnesium hydroxide can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle diameter distribution of magnesium hydroxide can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring device, and the median diameter can be measured as an average particle diameter. As a measurement sample, one in which magnesium hydroxide is 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, etc. can be used.

  Magnesium hydroxide is preferably surface-treated with a surface treatment agent from the viewpoint of further suppressing the haloing phenomenon. The surface treatment agent may, for example, be an alkoxysilane compound, an organosilazane compound or a titanate coupling agent. In particular, an alkoxysilane compound is preferable from the viewpoint of suppressing the haloing phenomenon.

The alkoxysilane compound preferably has a structure of “X—Si (OR ¹ ) _a (R ² ) _3-a ”. In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ² represents a hydrogen atom, a hydroxyl group or a halogen atom Or a hydrocarbon group. a represents an integer of 1 to 3; When a is 2 or 3, multiple R ^{1 s} may be the same or different. Moreover, when a is 1, several R < ² > may be the same and may be different. X represents an amino group, an epoxy group, a mercapto group, a vinyl group, an isocyanate group, a methacryl group, a urea group, a phenyl group, an alkyl group having 1 to 3 carbon atoms, and a group obtained by combining two or more of these groups.

  As an alkoxysilane compound, it is preferable that X in said Formula represents the group containing an amino group, a vinyl group, and an aminophenyl group from a viewpoint of suppressing a haloing phenomenon effectively. That is, the alkoxysilane compound is preferably an alkoxysilane compound having an amino group or an alkoxysilane compound having a vinyl group.

  Examples of commercially available alkoxysilane compounds include "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM 1003" (vinyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by Kogyo Co., Ltd., "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE 903" manufactured by Shin-Etsu Chemical Co., Ltd. Ethoxysilane), Shin-Etsu Chemical "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane), Shin-Etsu Chemical "KBM 103" (phenyltrimethoxysilane), Shin-Etsu Chemical "KBM-4803" (Long-chain epoxy type silane coupling agent) etc. It is. The alkoxysilane compounds may be used alone or in combination of two or more.

  The amount of the surface treatment agent is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and still more preferably 4 parts by mass with respect to 100 parts by mass of magnesium hydroxide from the viewpoint of effectively suppressing the haloing phenomenon. It is at most parts by mass, preferably at least 0.5 parts by mass, more preferably at least 0.6 parts by mass, and still more preferably at least 0.7 parts by mass.

The degree of surface treatment with a surface treatment agent can be evaluated by the amount of carbon per unit surface area of magnesium hydroxide. Carbon content per unit surface area of the magnesium hydroxide, from the viewpoint of improving dispersibility of the magnesium hydroxide, 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 the melt viscosity of the resin varnish and the increase of the melt viscosity in the form of a sheet, 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 preferable.

  The amount of carbon per unit surface area of magnesium hydroxide can be measured after washing the magnesium hydroxide after surface treatment with a surface treatment agent with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to surface-treated magnesium hydroxide to be subjected to ultrasonic cleaning at 25 ° C. for 5 minutes. After removing the supernatant and drying the solids, a carbon analyzer can be used to measure the amount of carbon per unit surface area of magnesium hydroxide. As a carbon analyzer, "EMIA-320V" etc. by Horiba, Ltd. can be used.

  From the viewpoint of effectively suppressing the haloing phenomenon, the content of the component (C) is preferably 2% by mass or more, more preferably 5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. More preferably, it is 10% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 38% by mass or less, and still more preferably 35% by mass or less from the viewpoint of improving the shape of the via hole.

<(D) silica>
The resin composition contains silica as component (D). By using (D) silica for the resin composition, the thermal expansion coefficient of the cured product of the resin composition can be reduced, and the dielectric loss tangent can also be reduced.

  Examples of (D) silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like, with spherical silica being preferred. The (D) silica may be used alone or in combination of two or more.

  (D) As commercially available products of silica, for example, "KE-P30" manufactured by Nippon Shokubai Co., Ltd., "SP60-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., "SP507-05"; "YC100C" manufactured by Admatechs Co., Ltd. “YA050C”, “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka; “Sylfil NSS-3N” manufactured by Tokuyama, “Sylfil NSS-4N”, “Sylfil NSS-5N”; "SC2500 SQ", "SO-C4", "SO-C2", "SO-C1";

  Usually, (D) silica is contained in the resin composition in the form of particles. (D) The average particle diameter of the silica is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1 .5 μm or less, 1.0 μm or less, 0.5 μm or less, 0.3 μm or less. (D) By the average particle diameter of silica being in the above range, even in the case of a thin film insulating layer, the insulation reliability becomes excellent, and the generation of the rounded portion of the wall surface of the via hole can be suppressed. . Also, usually, the circuit embedding property of the resin composition layer can be improved, or the surface roughness of the insulating layer can be reduced. The average particle diameter of (D) silica can be measured by the same method as the average particle diameter of (C) magnesium hydroxide.

The specific surface area of (D) silica, from the viewpoint of to facilitate the control of the shape of the via hole to achieve a good shape, preferably ^{15 m} 2 / g or more, more preferably ^{20 m} 2 / g or more, particularly preferably ^{30 m} 2 / It is more than g. The upper limit is not particularly limited, but preferably 60 m ² / g or less, 50 m ² / g or less, or 40 m ² / g or less. The specific surface area of silica can be measured by the BET method.

  (D) The silica may be treated with a surface treatment agent from the viewpoint of enhancing the moisture resistance and the dispersibility. As the surface treatment agent, the same as the surface treatment agent in (C) magnesium hydroxide can be used. The degree of surface treatment with the surface treatment agent is the same as in the case of (C) magnesium hydroxide.

  The content of the (D) silica is preferably 3% by mass or more, more preferably 10% by mass or more, and still more preferably from 100% by mass of the non-volatile component in the resin composition, from the viewpoint of obtaining desired effects. It is 20 mass% or more and 25 mass% or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less.

  The total content of (D) silica and (C) magnesium hydroxide is preferably 30% by mass, based on 100% by mass of non-volatile components in the resin composition, from the viewpoint of suppressing haloing more effectively. The content is more preferably 40% by mass or more, further preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

<(E) Thermoplastic resin>
The resin composition may further contain (E) a thermoplastic resin as an optional component, in addition to the components described above.

  Examples of the thermoplastic resin as component (E) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide imide resin, polyether imide resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin And polycarbonate resins, polyether ether ketone resins, polyester resins and the like. Among them, phenoxy resins are preferable from the viewpoint of obtaining the desired effects of the present invention remarkably and from the viewpoint of obtaining an insulating layer which is small in surface roughness and particularly excellent in adhesion to a conductor layer. The thermoplastic resins may be used alone or in combination of two or more.

  As the phenoxy resin, for example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene The phenoxy resin which has frame | skeleton and one or more types of frame | skeleton selected from the group which consists of trimethyl cyclohexane frame | skeleton is mentioned. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group and epoxy group.

  As a specific example of phenoxy resin, "1256" and "4250" (all are bisphenol A frame | skeleton containing phenoxy resin) by Mitsubishi Chemical Co., Ltd .; "YX8100" (bisphenol S frame | skeleton containing phenoxy resin) by Mitsubishi Chemical Co., Ltd .; Company's "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; “YL 7769 BH30”, “YL 6794”, “YL 7213”, “YL 7290” and “YL 748 2”;

  As polyvinyl acetal resin, polyvinyl formal resin, polyvinyl butyral resin is mentioned, for example, Polyvinyl butyral resin is preferable. As a specific example of polyvinyl acetal resin, "Electric charge butyral 4000-2", "electric charge butyral 5000-A", "electric charge butyral 6000-C", "electric charge butyral 6000-EP" made by Denki Kagaku Kogyo Co., Ltd .; Sekisui Chemical Co., Ltd. Elek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series;

  As a specific example of a polyimide resin, "Rika coat SN20" and "Rika coat PN20" by Shin Nippon Rika Co., Ltd. are mentioned. Specific examples of the polyimide resin also include a linear polyimide (polyimide described in JP-A-2006-37083) obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and a polysiloxane skeleton Modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386) can be mentioned.

  As a specific example of polyamide imide resin, Toyobo Co., Ltd. "Viromax HR11NN" and "Viromax HR16NN" are mentioned. Specific examples of the polyamideimide resin also include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  As a specific example of polyether sulfone resin, Sumitomo Chemical Co., Ltd. "PES5003P" etc. are mentioned.

  As a specific example of polyphenylene ether resin, oligo phenylene ether styrene resin "OPE-2St 1200" made by Mitsubishi Gas Chemical Co., Ltd., etc. may be mentioned.

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

  The weight average molecular weight (Mw) of the thermoplastic resin (E) is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of obtaining the desired effects of the present invention remarkably. And preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

  When (E) a thermoplastic resin is used, the amount of the (E) thermoplastic resin in the resin composition is preferably 100% by mass of the resin component in the resin composition from the viewpoint of obtaining the desired effects of the present invention. Is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass. It is less than mass%.

<(F) Hardening accelerator>
The resin composition may further contain (F) a curing accelerator as an optional component, in addition to the components described above.

  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. Among them, phosphorus-based curing accelerators, amine-based 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.

  As a phosphorus-based curing accelerator, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate Tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate and the like, and triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo Examples include (5,4,0) -undecene and the like, with preference given to 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene.

  Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 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′-undecylimidazolyl- (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-methyone And imidazole compounds such as 3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and adducts of the imidazole compound with an epoxy resin, and 2-ethyl-4-methylimidazole, 1-benzyl-2-ylimidazole. Phenylimidazole is preferred.

  A commercial item may be used as an imidazole series hardening accelerator, for example, "P200-H50" by Mitsubishi Chemical Corporation etc. is mentioned.

  As the guanidine-based curing accelerator, for example, dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine, diphenyl guanidine, trimethyl guanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1-( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

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

  When the curing accelerator (F) is used, the amount of the curing accelerator (F) in the resin composition is preferably 100% by mass of the resin component of the resin composition from the viewpoint of significantly achieving the desired effects of the present invention. Is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, preferably 1.5% by mass or less, more preferably 1% by mass or less Preferably it is 0.5 mass% or less.

<(G) Optional Additive>
The resin composition may further contain optional additives as optional components in addition to the components described above. Examples of such additives include organic fillers; resin additives such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and the like. These additives may be used alone or in combination of two or more.

<Thickness of Resin Composition Layer>
The resin composition layer is a layer formed of the above-described resin composition, and has a thickness equal to or less than a predetermined value. The specific thickness of the resin composition layer is usually 15 μm or less, preferably 14 μm or less, and more preferably 12 μm or less. Conventionally, the thickness of a resin composition layer for forming an insulating layer of a printed wiring board is generally thicker than this. On the other hand, when the present inventors made the resin composition layer of a general composition thin as described above, such a thin resin composition layer was not conventionally known to generate haloing phenomenon. I found that a problem arises. From the viewpoint of solving such new problems and contributing to thinning of the printed wiring board, the resin composition layer of the present invention is provided thin as described above. The lower limit of the thickness of the resin composition layer is arbitrary, and may be, for example, 1 μm or more and 3 μm or more.

<Characteristics of Resin Composition Layer>
By curing the resin composition layer of the present invention, a thin insulating layer formed of a cured product of the resin composition layer can be obtained. When a via hole is formed in the insulating layer, it is possible to suppress the haloing phenomenon that the resin of the insulating layer around the via hole is discolored. Hereinafter, these effects will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically showing an insulating layer 100 obtained by curing the resin composition layer according to the first embodiment of the present invention, together with the inner layer substrate 200. As shown in FIG. In FIG. 1, a cross section obtained by cutting the insulating layer 100 along a plane passing through the center 120 C of the bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100 is shown.

  As shown in FIG. 1, the insulating layer 100 according to the first embodiment of the present invention is a layer obtained by curing a resin composition layer formed on an inner layer substrate 200 including a conductor layer 210, It consists of hardened | cured material of the said resin composition layer. Further, a via hole 110 is formed in the insulating layer 100. The via hole 110 is generally formed in a forward tapered shape in which the diameter is larger as it is closer to the surface 100 U of the insulating layer 100 opposite to the conductor layer 210 and the diameter is smaller as it is closer to the conductor layer 210. It is formed in a columnar shape having a constant diameter in the thickness direction of 100. The via hole 110 is generally formed by irradiating a surface 100 U of the insulating layer 100 opposite to the conductor layer 210 with a laser beam to remove a part of the insulating layer 100.

  The bottom of the via hole 110 on the side of the conductor layer 210 is appropriately referred to as “via bottom” and denoted by reference numeral 120. And the diameter of this via bottom 120 is called bottom diameter Lb. In addition, an opening formed on the opposite side of the via hole 110 from the conductor layer 210 is appropriately referred to as “via top” and indicated by reference numeral 130. The diameter of the via top 130 is called a top diameter Lt. Generally, the planar shape of the via bottom 120 and the via top 130 viewed from the thickness direction of the insulating layer 100 is circular, but may be elliptical. When the planar shape of the via bottom 120 and the via top 130 is an elliptical shape, the bottom diameter Lb and the top diameter Lt respectively represent the major axis of the elliptical shape.

  At this time, as the taper ratio Lb / Lt (%) obtained by dividing the bottom diameter Lb by the top diameter Lt is closer to 100%, the shape of the via hole 110 is better. When the resin composition layer of the present invention is used, the shape of the via hole 110 can be easily controlled, so that the via hole 110 having a taper ratio Lb / Lt close to 100% can be realized. The taper ratio of the via hole means the ratio of the bottom diameter to the top diameter of the via hole.

For example, the resin composition layer is heated at 100 ° C. for 30 minutes and then cured by heating at 180 ° C. for 30 minutes to form an insulating layer 100 having a mask diameter of 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot When a via hole 110 having a top diameter Lt of 30 μm ± 2 μm is formed by irradiating CO ₂ laser light under the conditions of the number 2 and burst mode (10 kHz), the taper ratio Lb / Lt of the via hole 110 is preferably 75%. It can be 100%, more preferably 80% to 100%, particularly preferably 85% to 100%.

  The taper ratio Lb / Lt of the via hole 110 can be calculated from the bottom diameter Lb and the top diameter Lt of the via hole 110. Further, the bottom diameter Lb and the top diameter Lt of the via hole 110 appear in a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam) After cutting it out, it can measure by observing the cross section with an electron microscope.

  FIG. 2 schematically shows the surface 100U of the insulating layer 100 obtained by curing the resin composition layer according to the first embodiment of the present invention, on the side opposite to the conductor layer 210 (not shown in FIG. 2). It is a top view shown to.

  As shown in FIG. 2, when looking at the insulating layer 100 in which the via hole 110 is formed, a discolored portion 140 in which the insulating layer 100 is discolored may be observed around the via hole 110 due to the haloing phenomenon. The discolored portion 140 can be formed by resin deterioration at the time of forming the via hole 110, and is usually formed continuously from the via hole 110. Also, in many cases, the color changing part 140 is a whitening part.

FIG. 3 is a cross-sectional view schematically showing the roughened insulating layer 100 obtained by curing the resin composition layer according to the first embodiment of the present invention, together with the inner layer substrate 200. In FIG. 3, a cross section obtained by cutting the insulating layer 100 along a plane which passes through the center 120 C of the via bottom 120 of the via hole 110 and is parallel to the thickness direction of the insulating layer 100 is shown.
As shown in FIG. 3, when the insulating layer 100 in which the via hole 110 is formed is roughened, the insulating layer 100 of the discolored portion 140 is peeled from the conductor layer 210, and the gap portion 160 continued from the edge 150 of the via bottom 120. May be formed. The gap 160 is generally formed by eroding the discolored portion 140 during the roughening process.

  By using the resin composition layer of the present invention, the above-mentioned haloing phenomenon can be suppressed. Therefore, the size of the color changing portion 140 can be reduced. Thus, peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, and the size of the gap 160 can be reduced.

  As shown in FIG. 3, by using the resin composition layer of the present invention, the size of the discolored portion 140 can be reduced, and ideally the discolored portion 140 can be eliminated. The size of the discolored portion 140 can be evaluated by the haloing distance Wt from the edge 180 of the via top 130 of the via hole 110.

  The edge 180 of the via top 130 corresponds to the edge on the inner peripheral side of the discolored portion 140. The haloing distance Wt from the edge 180 of the via top 130 represents the distance from the edge 180 of the via top 130 to the edge 190 on the outer peripheral side of the discolored portion 140. It can be evaluated that the smaller the haloing distance Wt from the edge 180 of the via top 130, the more effectively the formation of the discolored portion 140 can be suppressed.

For example, the resin composition layer is heated at 100 ° C. for 30 minutes and then cured by heating at 180 ° C. for 30 minutes to form an insulating layer 100 having a mask diameter of 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot When a via hole 110 with a top diameter Lt of 30 μm ± 2 μm is formed by irradiating CO ₂ laser light under the conditions of the number 2 and burst mode (10 kHz), the haloing distance Wt from the edge 180 of the via top 130 is preferably Can be 6 μm or less, more preferably 5 μm or less.

  The haloing distance Wt from the edge 180 of the via top 130 can be measured by observation with an optical microscope.

  In addition, according to the study of the present inventor, it is generally found that the larger the diameter of the via hole 110, the larger the size of the color changing portion 140 tends to be. Therefore, the degree of suppression of the formation of the color changing portion 140 can be evaluated by the ratio of the size of the color changing portion 140 to the diameter of the via hole 110. For example, it can be evaluated by the haloing ratio Ht to the top radius Lt / 2 of the via hole 110. Here, the top radius Lt / 2 of the via hole 110 refers to the radius of the via top 130 of the via hole 110. The haloing ratio Ht to the top radius Lt / 2 of the via hole 110 is a ratio obtained by dividing the haloing distance Wt from the edge 180 of the via top 130 by the top radius Lt / 2 of the via hole 110. The smaller the haloing ratio Ht with respect to the top radius Lt / 2 of the via hole 110, the more effectively the formation of the discolored portion 140 is suppressed.

For example, the resin composition layer is heated at 100 ° C. for 30 minutes and then cured by heating at 180 ° C. for 30 minutes to form an insulating layer 100 having a mask diameter of 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot When a via hole 110 with a top diameter Lt of 30 μm ± 2 μm is formed by irradiating CO ₂ laser light under the conditions of the number 2 and the burst mode (10 kHz), the haloing ratio Ht to the top radius Lt / 2 of the via hole 110 is Preferably, it can be 45% or less, more preferably 40% or less, and still more preferably 35% or less.

  The haloing ratio Ht to the top radius Lt / 2 of the via hole 110 can be calculated from the top diameter Lt of the via hole 110 and the haloing distance Wt from the edge 180 of the via top 130 of the via hole 110.

  The edge 150 of the via bottom 120 corresponds to the edge on the inner circumferential side of the gap 160. Therefore, the distance Wb from the edge 150 of the via bottom 120 to the end on the outer circumferential side of the gap 160 (that is, the end on the far side from the center 120C of the via bottom 120) is the size of the gap 160 in the in-plane direction. Equivalent to. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100. In the following description, the distance Wb may be referred to as a haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110. The haloing distance Wb from the edge 150 of the via bottom 120 makes it possible to evaluate the degree of suppression of the haloing phenomenon. Specifically, it can be evaluated that the haloing phenomenon can be effectively suppressed as the haloing distance Wb from the edge 150 of the via bottom 120 is smaller.

For example, the resin composition layer is heated at 100 ° C. for 30 minutes and then cured by heating at 180 ° C. for 30 minutes to form an insulating layer 100 having a mask diameter of 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot By irradiating CO ₂ laser light under the conditions of the number 2, burst mode (10 kHz), a via hole 110 with a top diameter Lt of 30 μm ± 2 μm is formed. Then, it is dipped in a swelling solution at 60 ° C. for 10 minutes, then dipped in an oxidant solution at 80 ° C. for 20 minutes, and then dipped in a neutralization solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. When the resin composition layer of the present invention is used, the haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110 of the insulating layer 100 thus obtained is preferably 10 μm or less, more preferably 5 μm or less, and further Preferably, it can be 4 μm or less, particularly preferably 3 μm or less.

  The haloing distance Wb from the edge 150 of the via bottom 120 is such that a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120 C of the via bottom 120 appears using FIB (focused ion beam) After cutting it out, it can measure by observing the cross section with an electron microscope.

  Further, by using the resin composition layer of the present invention, since the shape of the via hole 110 of the insulating layer 100 before the roughening treatment can be easily controlled, the insulating layer 100 after the roughening treatment usually It is possible to control the shape easily. Therefore, even after the roughening treatment, the shape of the via hole 110 can be made excellent as in the case before the roughening treatment. Therefore, if the resin composition layer of the present invention is used, it is possible to realize the via hole 110 having a taper ratio Lb / Lt close to 100% in the insulating layer after the roughening treatment.

For example, the resin composition layer is heated at 100 ° C. for 30 minutes and then cured by heating at 180 ° C. for 30 minutes to form an insulating layer 100 having a mask diameter of 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot By irradiating CO ₂ laser light under the conditions of the number 2, burst mode (10 kHz), a via hole 110 with a top diameter Lt of 30 μm ± 2 μm is formed. Then, it is dipped in a swelling solution at 60 ° C. for 10 minutes, then dipped in an oxidant solution at 80 ° C. for 20 minutes, and then dipped in a neutralization solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. When the resin composition layer of the present invention is used, the taper ratio Lb / Lt of the via hole 110 formed in the insulating layer 100 thus obtained is preferably 76% to 100%, more preferably 80% to 100%. %, Particularly preferably 85% to 100%.

  The taper ratio Lb / Lt of the via hole 110 can be calculated from the bottom diameter Lb and the top diameter Lt of the via hole 110. Further, the bottom diameter Lb and the top diameter Lt of the via hole 110 appear in a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam) After cutting it out, it can measure by observing the cross section with an electron microscope.

  Furthermore, according to the study of the inventor of the present invention, it has been found that, generally, the larger the diameter of the via hole 110, the larger the size of the discolored portion 140, so the size of the gap 160 tends to be large. . Therefore, the degree of suppression of the haloing phenomenon can be evaluated by the ratio of the size of the gap 160 to the diameter of the via hole 110. For example, it can be evaluated by the haloing ratio Hb to the bottom radius Lb / 2 of the via hole 110. Here, the bottom radius Lb / 2 of the via hole 110 refers to the radius of the via bottom 120 of the via hole 110. Further, the haloing ratio Hb to the bottom radius Lb / 2 of the via hole 110 is a ratio obtained by dividing the haloing distance Wb from the edge 150 of the via bottom 120 by the bottom radius Lb / 2 of the via hole 110. The smaller the haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110, the more effectively the haloing phenomenon is suppressed.

For example, the resin composition layer is heated at 100 ° C. for 30 minutes and then cured by heating at 180 ° C. for 30 minutes to form an insulating layer 100 having a mask diameter of 1 mm, pulse width 16 μs, energy 0.2 mJ / shot, shot By irradiating CO ₂ laser light under the conditions of the number 2, burst mode (10 kHz), a via hole 110 with a top diameter Lt of 30 μm ± 2 μm is formed. Then, it is dipped in a swelling solution at 60 ° C. for 10 minutes, then dipped in an oxidant solution at 80 ° C. for 20 minutes, and then dipped in a neutralization solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. When the resin composition layer of the present invention is used, the haloing ratio Hb to the bottom radius Lb / 2 of the via hole 110 formed in the insulating layer 100 thus obtained is preferably 50% or less, more preferably 40. % Or less, more preferably 30% or less.

  The haloing ratio Hb to the bottom radius Lb / 2 of the via hole 110 can be calculated from the bottom diameter Lb of the via hole 110 and the haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110.

  In the process of manufacturing the printed wiring board, the via hole 110 is usually formed in a state in which another conductor layer (not shown) is not provided on the surface 100 U of the insulating layer 100 opposite to the conductor layer 210. Therefore, if the manufacturing process of the printed wiring board is known, it is possible to clearly recognize the structure in which the via bottom 120 is on the side of the conductor layer 210 and the via top 130 is open on the side opposite to the conductor layer 210. However, in the completed printed wiring board, conductor layers may be provided on both sides of the insulating layer 100. In this case, it may be difficult to distinguish between the via bottom 120 and the via top 130 depending on the positional relationship with the conductor layer. However, in general, the top diameter Lt of the via top 130 is equal to or larger than the bottom diameter Lb of the via bottom 120. Therefore, in the above case, it is possible to distinguish the via bottom 120 and the via top 130 according to the size of the diameter.

<Use of resin composition layer>
The resin composition layer of the present invention can be suitably used as a resin composition layer for forming an insulating layer of a printed wiring board (resin composition layer for forming an insulating layer of a printed wiring board), and It can use more suitably as a resin composition layer (The resin composition layer for interlayer insulation layer formation of a printed wiring board) for forming the interlayer insulation layer of a printed wiring board.

  In particular, from the viewpoint of suppressing the haloing phenomenon, the resin composition layer is suitable as a resin composition layer (resin composition layer for forming an insulating layer having a via hole) for forming an insulating layer having a via hole. Among them, it is particularly suitable as a resin composition layer for forming an insulating layer having a via hole with a top diameter of 35 μm or less.

[Resin sheet]
The resin sheet of the present invention comprises a support and the resin composition layer of the present invention provided on the support.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper, 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, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter abbreviated as "PEN"). Etc.), polycarbonates (hereinafter sometimes abbreviated as "PC"), acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA"), cyclic polyolefins, triacetyl cellulose "TAC" may be abbreviated), polyether sulfide (hereinafter sometimes abbreviated as "PES"), polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, copper foil, aluminum foil etc. are mentioned as metal foil, for example, 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.) You may use.

  The surface of the support to be bonded to the resin composition layer may be subjected to treatments such as mat treatment, corona treatment, antistatic treatment and the like.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. As the release agent used for the release layer of the support with release layer, for example, one or more types of release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin can be mentioned. . The release layer-provided support may be a commercially available product. For example, “SK-1” manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component AL-5 "," AL-7 ";" Lumirror T60 "manufactured by Toray Industries, Inc .;" Purex "manufactured by Teijin Limited;" Uni-Pel "manufactured by Unitika; and the like.

  The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. In addition, when using the support body with a release layer, it is preferable that the thickness of the support body with a release layer is the said range.

  Moreover, the resin sheet may contain arbitrary layers other than a support body and a resin composition layer as needed. As such an optional layer, there may be mentioned, for example, a protective film according to a support, etc., provided on the side of the resin composition layer not bonded to the support (that is, the side opposite to the support). Be Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By the protective film, it is possible to suppress adhesion of dust and the like to the surface of the resin composition layer and scratches.

  The resin sheet is prepared, for example, a resin varnish containing an organic solvent and a resin composition, the resin varnish is applied on a support using a coating apparatus such as a die coater, and further dried to obtain a resin composition layer. It can be manufactured by forming.

  Organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitol such as cellosolve and butyl carbitol Solvents; Aromatic hydrocarbon solvents such as toluene and xylene; Amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. The organic solvents may be used alone or in combination of two or more.

  Drying may be carried out by a method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it changes also with the boiling points of the organic solvent in a resin varnish, when using the resin varnish containing 30 mass%-60 mass% organic solvent, for example, resin composition by making it dry at 50 degreeC-150 degreeC for 3 minutes-10 minutes Object layer can be formed.

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

[Printed wiring board]
The printed wiring board of the present invention includes the insulating layer formed of the cured product of the thin resin composition layer as described above. Also, this insulating layer can suppress the haloing phenomenon. Therefore, by using the resin composition layer of the present invention, thinning of a printed wiring board can be achieved while suppressing the haloing phenomenon.

  The via holes are usually provided to conduct the conductor layers provided on both sides of the insulating layer having the via holes. Therefore, the printed wiring board of the present invention usually includes a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer. Then, a via hole is formed in the insulating layer, and the first conductor layer and the second conductor layer can be electrically connected through the via hole.

By utilizing the advantage of the resin composition layer that the haloing phenomenon can be suppressed and a via hole of a good shape can be formed, it is possible to realize a specific printed wiring board which has hitherto been difficult to realize. it can. The specific printed wiring board is 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 following requirements (i) to (iv) are all satisfied.
(I) The thickness of the insulating layer is 15 μm or less.
(Ii) The insulating layer has a via hole with a top diameter of 35 μm or less.
(Iii) The haloing distance from the edge of the via top of the via hole is 5 μm or less.
(Iv) The haloing ratio to the top radius of the via hole is 35% or less.

  Hereinafter, the specific printed wiring board will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view of a printed wiring board 300 according to a second embodiment of the present invention. In FIG. 4, a cross section obtained by cutting the printed wiring board 300 along a plane passing through the center 120 C of the via bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100 is shown. Moreover, in FIG. 4, the site | part corresponded to the element described in FIGS. 1-3 attaches and shows the code | symbol similar to having used in FIGS. 1-3.

  As shown in FIG. 4, the specific printed wiring board 300 according to the second embodiment of the present invention includes the first conductor layer 210, the second conductor layer 220, and the first conductor layer 210 and the second conductor. It includes an insulating layer 100 formed between the layer 220 and the layer 220. In the insulating layer 100, a via hole 110 is formed. Also, generally, the second conductor layer 220 is provided after the via hole 110 is formed. Therefore, the second conductor layer 220 is usually formed not only in the surface 100 U of the insulating layer 100 but also in the via hole 110, and the first conductor layer 210 and the second conductor layer 220 are electrically connected through the via hole 110. doing.

  The thickness T of the insulating layer 100 included in the specific printed wiring board 300 is usually 15 μm or less, preferably 12 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. Since the specific printed wiring board 300 has the thin insulating layer 100 in this manner, thinning of the specific printed wiring board 300 itself can be achieved. The lower limit of the thickness T of the insulating layer 100 is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more, from the viewpoint of enhancing the insulation performance of the insulating layer 100. Here, the thickness T of the insulating layer 100 represents the dimension of the insulating layer 100 between the first conductor layer 210 and the second conductor layer 220, and the first conductor layer 210 or the second conductor layer 220. It does not represent the dimension of the insulating layer 100 at the position where there is no. The thickness T of the insulating layer 100 generally corresponds to the distance between the main surface 210U of the first conductor layer 210 and the main surface 220D of the second conductor layer 220 facing each other through the insulating layer 100, and , The depth of the via hole 110.

  The top diameter Lt of the via hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is usually 35 μm or less, preferably 33 μm or less, and particularly preferably 32 μm or less. Since the specific printed wiring board 300 includes the insulating layer 100 having the via hole 110 having a small top diameter Lt in this manner, it is possible to promote miniaturization of the wiring including the first conductor layer 210 and the second conductor layer 220. it can. The lower limit of the top diameter Lt of the via hole 110 is preferably 3 μm or more, more preferably 10 μm or more, and particularly preferably 15 μm or more from the viewpoint of easily forming the via hole 110.

  The haloing distance Wt from the edge 180 of the via top 130 of the via hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 5 μm or less, preferably 4 μm or less. The specific printed wiring board 300 has such a small haloing distance Wt from the edge 180 of the via top 130. Therefore, the specific printed wiring board 300 can generally improve the reliability of the conduction between the first conductor layer 210 and the second conductor layer 220.

  The haloing ratio Ht to the top radius Lt / 2 of the via hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is usually 35% or less, preferably 30% or less, and more preferably 25% or less. In the specific printed wiring board 300, the haloing ratio Ht with respect to the top radius Lt / 2 is thus small, and hence the peeling of the insulating layer 100 from the first conductor layer 210 is small. As described above, the specific printed wiring board 300 including the insulating layer 100 having a small haloing ratio Ht can generally improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220. The lower limit of the haloing ratio Ht to the top radius Lt / 2 is ideally zero but is usually 5% or more.

  The haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 5 μm or less, preferably 4 μm or less, and more preferably 3 μm or less. In the specific printed wiring board 300, the haloing distance Wb from the edge 150 of the via bottom 120 is thus small, so that the peeling of the insulating layer 100 from the first conductor layer 210 is small. Therefore, the specific printed wiring board 300 can generally improve the reliability of the conduction between the first conductor layer 210 and the second conductor layer 220.

  The haloing ratio Hb to the bottom radius Lb / 2 of the via hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is usually 35% or less, preferably 30% or less, and more preferably 25% or less. In the specific printed wiring board 300, the haloing ratio Hb to the bottom radius Lb / 2 is thus small, and therefore the peeling of the insulating layer 100 from the first conductor layer 210 is small. As described above, the specific printed wiring board 300 including the insulating layer 100 having a small haloing ratio Hb can generally improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220. The lower limit of the haloing ratio Hb to the bottom radius Lb / 2 is ideally zero, but is usually 5% or more.

  The taper ratio Lb / Lt (%) of the via hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is usually 80% to 100%. The specific printed wiring board 300 includes the insulating layer 100 having the well-shaped via hole 110 with a high taper ratio Lb / Lt. Therefore, the specific printed wiring board 300 can generally improve the reliability of the conduction between the first conductor layer 210 and the second conductor layer 220.

  The number of via holes 110 included in the insulating layer 100 included in the specific printed wiring board 300 may be one or two or more. When the insulating layer 100 has two or more via holes 110, a portion thereof may satisfy the requirements (i) to (iv), but it is preferable that all of the requirements satisfy the requirements (i) to (iv) . Also, for example, it is preferable that the five via holes 110 randomly selected from the insulating layer 100 satisfy the requirements (i) to (iv) on average.

  The specific printed wiring board 300 described above can be realized by forming the insulating layer 100 with the cured product of the resin composition layer of the present invention. At this time, the planar shapes of the via bottom 120 and the via top 130 of the via hole 110 formed in the insulating layer 100 are arbitrary, but are usually circular or elliptical, preferably circular.

A printed wiring board such as a specific printed wiring board can be manufactured, for example, by using a resin sheet and performing a manufacturing method including the following steps (I) to (IV).
(I) A step of laminating a resin sheet on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate.
(II) A step of heat curing the resin composition layer to form an insulating layer.
(III) forming a via hole in the insulating layer.
(IV) A step of roughening the insulating layer.

  The "inner layer substrate" used in step (I) is a member to be a substrate of a printed wiring board. Examples of the inner layer substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate and the like. Usually, as the inner layer substrate, one having a conductor layer on one side or both sides is used. Then, an insulating layer is formed on the conductor layer. The conductor layer may be patterned, for example, to function as a circuit. An inner layer substrate in which a conductor layer is formed as a circuit on one side or both sides of the substrate may be referred to as an "inner layer circuit board". In addition, an intermediate product to which an insulating layer and / or a conductor layer is to be further formed when producing a printed wiring board is also included in the "inner layer substrate". When the printed wiring board is a component built-in circuit board, an inner layer substrate containing components may be used.

  The lamination of the inner layer substrate and the resin sheet can be performed, for example, by bonding the resin composition layer to the inner layer substrate by thermocompression bonding of the resin sheet to the inner layer substrate from the support side. Examples of a member for heating and pressing a resin sheet to the inner layer substrate (hereinafter sometimes referred to as “heat-pressed member”) include a heated metal plate (SUS mirror plate etc.) or a metal roll (SUS roll). . In addition, it is preferable to press via an elastic material such as heat resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate, instead of directly pressing the heat pressure-bonding member on the resin sheet.

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

  Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure type laminator manufactured by Nikkiso Co., Ltd., a vacuum applicator manufactured by Nikko Materials, a batch type vacuum pressure laminator, etc. may be mentioned.

  After lamination, the laminated resin sheet may be subjected to a smoothing treatment by, for example, pressing the heat pressure-bonding member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. In addition, you may perform lamination | stacking and smoothing processing continuously using said commercially available vacuum laminator.

  In the step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions employed in forming the insulating layer of the printed wiring board may be arbitrarily used.

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

  Before heat curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C. or more and less than 120 ° C. (preferably 60 ° C. or more and 115 ° C. or less, more preferably 70 ° C. or more and 110 ° C. or less). May be preheated usually 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 the step (III), via holes are formed in the insulating layer. Examples of the method for forming the via holes include laser light irradiation, etching, mechanical drilling and the like. Among them, since the haloing phenomenon is generally liable to occur, irradiation of laser light is preferable from the viewpoint of effectively utilizing the effect of suppressing the haloing phenomenon.

The irradiation of the laser light can be performed using, for example, a laser processing machine having a laser light source such as a carbon dioxide gas laser, a YAG laser, or an excimer laser as a light source. As a laser processing machine which can be used, for example, a CO ₂ laser processing machine "LC-2k212 / 2C" manufactured by Via Mechanics, 605 GTW III (-P) manufactured by Mitsubishi Electric Corp., a laser processing machine manufactured by Matsushita Welding Systems Co., Ltd., etc. Can be mentioned.

  The irradiation conditions of the laser light such as the wavelength of the laser light, the number of pulses, the pulse width, and the output are not particularly limited, and appropriate conditions may be set according to the type of the laser light source.

  In the step (IV), the insulating layer is roughened. The procedure and conditions of the roughening treatment are not particularly limited, and any procedure and conditions used in forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling process with a swelling solution, a roughening process with an oxidizing agent, and a neutralization process with a neutralizing solution in this order.

  Although it does not specifically limit as a swelling liquid, For example, an alkaline solution, surfactant solution etc. are mentioned, Preferably an alkaline solution is mentioned. As the alkaline solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a swelling liquid marketed, "Swelling dip security G" and "Swelling dip security SBU" by Atotech Japan Ltd., etc. are mentioned, for example. Moreover, swelling liquid may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing an insulating layer in the swelling liquid of 30 degreeC-90 degreeC for 1 minute-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 for 5 minutes to 15 minutes in a swelling liquid at 40 ° C to 80 ° C.

  Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganic acid solution which melt | dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. Moreover, an oxidizing agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in the oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. Moreover, as for the density | concentration of the permanganate in alkaline permanganic acid solution, 5 mass%-10 mass% are preferable. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd.

  As a neutralization liquid, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Security G" manufactured by Atotech Japan Co., Ltd. may be mentioned. Further, one type of neutralization solution may be used alone, or two or more types may be used in combination at an arbitrary ratio. The treatment with the neutralization solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralization solution at 30 ° C. to 80 ° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the target subjected to the roughening treatment with the oxidizing agent in a neutralization solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  By the way, the support may be removed between the step (I) and the step (II), or may be removed between the step (II) and the step (III), and the step (III) and the step It may be removed between IV) and may be removed after step (IV).

  The method for producing a printed wiring board may further include the step of forming a (V) conductor layer. This process (V) may be implemented according to the various methods used for manufacture of a printed wiring board.

  Step (V) is a step of forming a conductor layer. The conductor material used for a conductor layer is not specifically 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. As the alloy layer, for example, a layer formed of an alloy of two or more types of metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy and a copper-titanium alloy) can be mentioned. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, copper single metal layer, or nickel-chromium alloy, copper from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc. Nickel alloy, an alloy layer of copper-titanium alloy is preferable. Furthermore, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper is particularly preferable.

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

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

  The conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Among them, the semiadditive method is preferable from the viewpoint of simplicity of production.

  Hereinafter, the example which forms a conductor layer by a semiadditive method is shown. First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  In addition, if necessary, the formation of the insulating layer and the conductor layer in the steps (I) to (V) may be repeated to manufacture a multilayer printed wiring board.

[Semiconductor device]
A semiconductor device of the present invention includes the above printed wiring board. This semiconductor device can be manufactured using a printed wiring board.

  Examples of the semiconductor device include various semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras, televisions and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft and the like) and the like.

  The semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) at a conductive portion of a printed wiring board. The "conductive location" is a "location for transmitting an electrical signal in a printed wiring board", and the location may be a surface or an embedded location. In addition, as the semiconductor chip, an electric circuit element made of a semiconductor can be used arbitrarily.

  The mounting method of the semiconductor chip at the time of manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Examples of mounting methods include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting using a nonconductive film (NCF) Methods, etc. Here, "the mounting method using a bumpless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board". It is.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass" unless otherwise specified. Moreover, the operation described below was performed in an environment of normal temperature and normal pressure unless otherwise specified.

<Magnesium hydroxide used>
Magnesium hydroxide 1: Magnesium hydroxide ("Kojima Chemical Industry Co., Ltd." EP-4A ", average particle diameter 1.1 μm (inorganic material treated)) 100 parts, Shin-Etsu Chemical" KBM 573 "(N-phenyl) 3-Aminopropyltrimethoxysilane) surface-treated with 3 parts.
Magnesium hydroxide 2: Magnesium hydroxide ("EP-4A" manufactured by Kamishima Chemical Industry Co., Ltd., average particle diameter: 1.1 μm (inorganic treated)), 100 parts of "KBM 1003" manufactured by Shin-Etsu Chemical Co., Ltd. (vinyltrimethoxy) Silane surface-treated with 3 parts.

<Used silica>
Silica 1: Spherical silica ("UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter 0.1 μm, specific surface area 30.7 m ² / g) relative to 100 parts of "KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd. (N- Surface-treated with 2 parts of phenyl-3-aminopropyltrimethoxysilane).
Silica 2: Spherical silica ("UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter 0.1 μm, specific surface area 30.7 m ² / g) relative to 100 parts of "KBM 1003" manufactured by Shin-Etsu Chemical Co., Ltd. Surface-treated with 2 parts of methoxysilane).
Silica 3: Spherical silica ("KE-P30" manufactured by Nippon Shokuhin Co., Ltd., average particle diameter 0.3 μm, specific surface area 35 m ² / g) relative to 100 parts of "KBM 573" manufactured by Shin-Etsu Chemical (N-phenyl-3) -Surface treated with 2 parts of aminopropyltrimethoxysilane).
Silica 4: Spherical silica ("KE-P30" manufactured by Nippon Shokuhin Co., Ltd., average particle diameter 0.3 μm, specific surface area 35 m ² / g) 100 parts by Shin-Etsu Chemical "KBM 1003" (vinyltrimethoxysilane) Surface-treated with 2 parts.

Example 1
6 parts of bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin ("NSN475V" manufactured by Nippon Steel Sumikin Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical's "YL 7760", 15 parts epoxy equivalent epoxy resin (Mitsubishi Chemical's "ZX1658GS", epoxy equivalent about 135) 2 parts, phenoxy resin (Mitsubishi Chemical's "YL 7500 BH30", solid content Two parts of a 1: 1 solution of 30% by mass cyclohexanone: methyl ethyl ketone (MEK), Mw = 44000) was dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, 6 parts of active ester-based curing agent ("EXB-8000L-65TM" manufactured by DIC, active group equivalent weight about 220, non-volatile component 65 mass% toluene: MEK solution) A triazine skeleton-containing cresol novolac curing agent ("LA-3018-50P" manufactured by DIC, a hydroxyl equivalent weight of about 151, a solid content of 50% in 2-methoxypropanol solution) 4 parts, magnesium hydroxide 1 15 parts, silica 1 35 parts of this and 0.05 parts of an amine curing accelerator (4-dimethylaminopyridine (DMAP)) are mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO) The resin composition 1 was prepared.

Example 2
In the preparation of resin composition 1, the amount of magnesium hydroxide 1 was changed from 15 parts to 25 parts, and the amount of silica 1 was changed from 35 parts to 25 parts. A resin composition 2 was prepared in the same manner as the preparation of the resin composition 1 except for the above matters.

Example 3
In the preparation of resin composition 1, 15 parts of magnesium hydroxide 1 were changed to 15 parts of magnesium hydroxide 2. A resin composition 3 was prepared in the same manner as the preparation of the resin composition 1 except for the above matters.

Example 4
In the preparation of resin composition 1, 35 parts of silica 1 were changed to 35 parts of silica 2. A resin composition 4 was prepared in the same manner as the preparation of the resin composition 1 except for the above matters.

Example 5
In the preparation of resin composition 1, 35 parts of silica 1 were changed to 35 parts of silica 3. A resin composition 5 was prepared in the same manner as the preparation of the resin composition 1 except for the above matters.

Example 6
In the preparation of resin composition 1, 35 parts of silica 1 were changed to 35 parts of silica 4. A resin composition 6 was prepared in the same manner as the preparation of the resin composition 1 except for the above matters.

Comparative Example 1
In preparation of the resin composition 1, the amount of the silica 1 was changed from 35 parts to 50 parts without containing the magnesium hydroxide 1. A resin composition 7 was prepared in the same manner as the preparation of the resin composition 1 except for the above matters.

Comparative Example 2
In the preparation of resin composition 7, 50 parts of silica 1 were changed to 50 parts of silica 2. Resin composition 8 was prepared in the same manner as preparation of resin composition 7 except for the above matters.

Comparative Example 3
In the preparation of resin composition 7, 50 parts of silica 1 were changed to 50 parts of silica 3. Resin composition 9 was prepared in the same manner as preparation of resin composition 7 except for the above matters.

Comparative Example 4
In the preparation of resin composition 7, 50 parts of silica 1 were changed to 50 parts of silica 4. Resin composition 10 was prepared in the same manner as preparation of resin composition 7 except for the above matters.

The component used for preparation of the resin compositions 1-10, and its compounding quantity were shown in the following table. Abbreviations etc. in the following table are as follows.
YX4000HK: Bixylenol type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight about 185
ESN 475 V: Naphthalene type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: approximately 332
YL 7760: Bisphenol AF type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 238
ZX1658GS: Cyclohexane type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight about 135
LA-3018-50P: triazine skeleton-containing cresol novolac curing agent, manufactured by DIC, 2-methoxypropanol solution EXB-8000L-65M having a hydroxyl content of about 151 and a solid content of 50%: active ester curing agent, manufactured by DIC, MEK solution YX 7 500 BH 30: phenoxy resin, non-volatile component 65% by mass equivalent weight of active group equivalent: phenoxy resin, 30% by weight cyclohexanone with solid content 30% by weight: 1: 1 solution of methyl ethyl ketone (MEK), weight average molecular weight 44000
DMAP: Amine curing accelerator, total content of 4-dimethylaminopyridine (in terms of resin component): Amount of component (C) and component (D) removed from non-volatile components contained in the resin composition (B) component Total content of: total content of component (B) when resin component in resin composition is 100% by mass Content of active ester-based curing agent: resin component in resin composition is 100% by mass The total content of the components (C) and (D) of the active ester curing agent in the case: The total of the components (C) and (D) when the nonvolatile component in the resin composition is 100% by mass Content (C) Component Content: Content of (C) Component When Nonvolatile Component in Resin Composition is 100% by Mass

<Production of resin sheet>
A PET film (“Lumirror R80” manufactured by Toray Industries, thickness 38 μm, softening point 130 ° C., “releasing PET”) which has been subjected to release treatment with an alkyd resin-based release agent (“AL-5” manufactured by Lintec Corporation) as a support Prepared.

  Each resin composition is uniformly coated with a die coater on release PET so that the thickness of the resin composition layer after drying is 10 μm, and the release is performed at 70 ° C. to 95 ° C. for 2 minutes. A resin composition layer was obtained on PET. Then, the rough surface of a polypropylene film ("Alfan MA-411" manufactured by Oji F-TEX, thickness 15 μm) is bonded to the resin composition layer as a protective film on the surface of the resin sheet not bonded to the support. Stacked. Thereby, resin sheet A which consists of mold release PET (support body), a resin composition layer, and a protective film in order was obtained.

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

<Evaluation of haloing after laser via processing>
-Preparation of evaluation substrate A-
(1) Copper-clad laminate As a copper-clad laminate, a glass cloth-based epoxy resin double-sided copper-clad laminate in which copper foil layers are laminated on both sides (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Co., Ltd. "HL 832 NSF LCA" (255 x 340 mm size) was prepared.

(2) Lamination of resin sheet The protective film is peeled off from each resin sheet A prepared using resin compositions 1 to 10, and a batch type vacuum pressure laminator (manufactured by Nikko Materials, 2 stage build up laminator, CVP 700) The laminate was laminated on both sides of the copper-clad laminate so that the resin composition layer was in contact with the copper-clad laminate. The lamination was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and pressure bonding at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Next, 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 placed in an oven at 100 ° C. for 30 minutes, then transferred to an oven at 180 ° C. and thermally cured for 30 minutes. A layer was formed and release PET was peeled off. This is a cured substrate A.

(4) Laser via processing Using a CO ₂ laser processing machine "605 GT W III (-P)" manufactured by Mitsubishi Electric Corp., a laser is irradiated from above the insulating layer to form a via hole with a top diameter (diameter) of 30 μm in the insulating layer. did. The laser irradiation conditions were a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, a shot number of 2, and a burst mode (10 kHz). This is called a via processed substrate A.

(5) Step of Roughening Treatment The via processed substrate A was subjected to desmearing treatment as roughening treatment. In addition, as a desmear process, the following wet desmear process was implemented.

Wet desmear treatment:
Swelling solution ("Swelling dip Security Gent P" manufactured by Atotech Japan Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 10 minutes, and then an oxidant solution ("Concentrate Compact CP" manufactured by Atotech Japan Ltd.) Finally, the solution is neutralized with an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4% at 80 ° C for 20 minutes. Finally, the neutralization solution ("Reduction Solution Securityg P" manufactured by Atotech Japan, sulfuric acid aqueous solution) After immersion at 40 ° C. for 5 minutes, it was dried at 80 ° C. for 15 minutes. This is referred to as a roughened substrate A.

<Measurement of via diameter after desmearing>
Cross-sectional observation of the roughened substrate A was performed using an FIB-SEM composite device (“SMI3050SE” manufactured by SII Nano Technology Inc.). In detail, the cross section in the perpendicular direction of the laser via was scraped off by FIB (focused ion beam), and the diameter of the laser via after desmear treatment was measured from the cross-sectional SEM image. The diameter of the via top after desmearing was measured from five cross-sectional SEM images randomly selected for each sample, and the average value was defined as the via top diameter Lt (μm), and the results are shown in the following table.

<Measurement of haloing distance after roughening process>
The roughened substrate A was observed with an optical microscope ("KH 8700" manufactured by HIROX Co., Ltd.). In detail, the insulating layer around the via hole was observed from the top of the roughened substrate A using an optical microscope (CCD). This observation was performed by focusing the light microscope on the via top. As a result of observation, a donut shaped haloing portion in which the insulating layer was discolored white was observed continuously from the edge of the via top of the via hole around the via hole. Therefore, the radius r1 of the via top of the via hole (corresponding to the inner circumferential radius of the haloing portion) r1 and the outer radius r2 of the haloing portion are measured from the observed image, and the difference r2 between the radius r1 and the radius r2 -R1 was calculated as the haloing distance from the edge of the via top at the measurement point.

  The above measurements were performed at five randomly selected via holes. Then, the average of the measured values of the haloing distances of the five via holes measured was adopted as the haloing distance Wt from the edge of the via top of the sample.

  In the following table, the haloing ratio Ht is the ratio (Ht) of the haloing distance Wt from the edge of the via top after the roughening treatment to the radius (Lt / 2) of the via top of the via hole after the roughening treatment When the haloing ratio Ht was 35% or less, it was determined as “o”, and when the haloing ratio Ht was larger than 35%, it was determined as “x”.

  In Examples 1 to 6, it is understood that the haloing ratio Ht is small even when the insulating layer is formed using the resin composition layer having a small thickness of 10 μm. From this result, it has been confirmed that the resin composition layer of the present invention can realize an insulating layer capable of suppressing the haloing phenomenon even when the thickness is thin. Moreover, Examples 1-6 have confirmed that it is excellent also in a flame retardance.

  In Examples 1 to 6, even when the components (E) to (F) are not contained, it is confirmed that the results similar to those of the above-described examples result, although the degree is different.

100 Insulating layer 100 U Insulating layer opposite to conductor layer 110 Via hole 120 Via bottom 120 C Center of via bottom 130 Via top 140 Discolored portion 150 Via bottom edge of via hole 160 Gap portion 170 Outer edge of gap portion 180 Via hole Edge of via top 190 Edge on outer peripheral side of discolored portion 200 Inner layer substrate 210 Conductor layer (first conductor layer)
210U First conductor layer main surface 220 Second conductor layer 220D Second conductor layer main surface 300 Printed wiring board Lb Bottom diameter of via hole Lt Top diameter of via hole T Thickness of insulating layer Wt Halo from edge of via top Hinging distance from edge of Wb via bottom

Claims (16)

A resin composition layer containing a resin composition and having a thickness of 15 μm or less,
A resin composition layer, wherein the resin composition comprises (A) epoxy resin, (B) curing agent, (C) magnesium hydroxide, and (D) silica.   The resin composition layer according to claim 1, wherein an average particle diameter of the component (D) is 3 μm or less.   The resin composition layer according to claim 1, wherein an average particle diameter of the component (D) is 0.3 μm or less.   The resin composition according to any one of claims 1 to 3, wherein the content of the component (D) is 3% by mass or more and 50% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Object layer.   The component (B) is one or more selected from a phenol-based curing agent, an active ester-based curing agent, a cyanate ester-based curing agent, and a benzoxazine-based curing agent according to any one of claims 1 to 4. Resin composition layer.   The resin composition according to any one of claims 1 to 5, wherein the content of the component (A) is 3% by mass or more and 50% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Object layer.   The resin composition layer according to any one of claims 1 to 6, wherein the component (C) is surface-treated with a surface treatment agent.   The resin composition layer according to claim 7, wherein the surface treatment agent is an alkoxysilane compound.   The resin composition layer according to claim 8, wherein the alkoxysilane compound has an amino group or a vinyl group.   The resin composition layer according to any one of claims 7 to 9, wherein the amount of the surface treatment agent is 5 parts by mass or less with respect to 100 parts by mass of magnesium hydroxide.   The resin composition according to any one of claims 1 to 10, wherein the content of the component (C) is 2 mass% or more and 40 mass% or less when the nonvolatile component in the resin composition is 100 mass%. Object layer.   The resin composition layer according to any one of claims 1 to 11, which is a resin composition layer for an insulating layer of a multilayer printed wiring board.   The resin composition layer according to any one of claims 1 to 12, which is for forming an insulating layer having a via hole having a top diameter of 35 μm or less.   The resin sheet containing a support body and the resin composition layer of any one of Claims 1-13 provided on the support body.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition layer of any one of Claims 1-13.   A semiconductor device comprising the printed wiring board according to claim 15.

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