JP2020075977A - Resin composition - Google Patents

Abstract

To provide a resin composition that can suppress haloing phenomenon and can produce an insulation layer excellent in insulation properties when forming a thin resin composition layer.SOLUTION: The resin composition includes (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler having a specific surface area of 15 m/g or more, (D) a compound represented by formula (1) as given below and (E) a phosphazene compound. Formula (1) is (X-R)Si(OR)(in formula (1), X's each independently represent an amino group which may have a substituent; R's each independently represent a 4C or more divalent aliphatic hydrocarbon group which may have a substituent; R's each independently represent a hydrogen atom or a 1-3C monovalent aliphatic hydrocarbon group; and s and t each independently represent an integer which satisfies 1≤s≤3, 1≤t≤3 and s+t=4.)SELECTED DRAWING: Figure 1

Description

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

  In recent years, printed wiring boards have been further reduced in thickness in order to achieve miniaturization of electronic devices. Along with this, miniaturization of wiring circuits on the inner layer substrate has been promoted. For example, Patent Document 1 describes a resin sheet including a support and a resin composition layer, which is compatible with fine wiring.

JP, 2017-36377, A

  Generally, an insulating layer of a printed wiring board is formed by curing a resin composition layer containing a resin composition. The present inventors have studied thinning the insulating layer by thinning the resin composition layer in order to further reduce the size and thickness of the electronic device.

  As a result of the above-mentioned examination, the inventors have found that when a thin resin composition layer is applied to an insulating layer, a roughening treatment occurs largely when a roughening treatment is performed after forming a via hole in the insulating layer. Found out. Here, the haloing phenomenon means that delamination occurs between the insulating layer and the inner layer substrate around the via hole. Such a haloing phenomenon usually occurs when the insulating layer around the via hole is discolored when the via hole is formed, and the discolored portion is eroded during the roughening treatment. From the viewpoint of increasing the reliability of conduction between layers of the printed wiring board, it is desired to suppress this haloing phenomenon.

  Further, as a result of the above-mentioned examination, the present inventors have found that when the insulating layer is thinned, the insulating property of the insulating layer may deteriorate.

  The present invention was devised in view of the above problems, and a resin composition capable of suppressing a haloing phenomenon and obtaining a thin insulating layer having excellent insulating properties; a resin containing the resin composition described above. (EN) A resin sheet provided with a composition layer; and a printed wiring board and a semiconductor device containing a cured product of the above resin composition.

The present inventors have earnestly studied to solve the above problems. As a result, the present inventors have found that (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler having a specific surface area of a predetermined value or more, (D) a compound represented by the formula (1) described later. , And (E) a resin composition containing a combination of a phosphazene compound, was found to be able to solve the above problems, and completed the present invention.
That is, the present invention includes the following.

（式（２）において、Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有していてもよいアリール基を示し、ｎは、１〜２３の整数を示す。）
〔５〕 （Ｃ）成分の量が、樹脂組成物中の不揮発成分１００質量％に対して、３０質量％以上９０質量％以下である、〔１〕〜〔４〕のいずれか一項に記載の樹脂組成物。
〔６〕 （Ｅ）成分の量が、樹脂組成物中の不揮発成分１００質量％に対して、０．１質量％以上１０質量％以下である、〔１〕〜〔５〕のいずれか一項に記載の樹脂組成物。
〔７〕 プリント配線板の絶縁層形成用である、〔１〕〜〔６〕のいずれか一項に記載の樹脂組成物。
〔８〕 支持体と、
支持体上に設けられた、〔１〕〜〔７〕のいずれか一項に記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
〔９〕 樹脂組成物層の厚みが、１５μｍ以下である、〔８〕に記載の樹脂シート。
〔１０〕 〔１〕〜〔７〕のいずれか一項に記載の樹脂組成物の硬化物で形成された絶縁層を含む、プリント配線板。
〔１１〕 〔１０〕記載のプリント配線板を含む、半導体装置。 [1] (A) Epoxy resin, (B) curing agent, (C) inorganic filler having a specific surface area of 15 m ² / g or more, (D) compound represented by the following formula (1), and (E) A resin composition containing a phosphazene compound.
(X-R ^a ) _s Si (OR ^b ) _t (1)
(In formula (1),
X's each independently represent an amino group which may have a substituent,
R ^a's each independently represent a divalent aliphatic hydrocarbon group having 4 or more carbon atoms which may have a substituent,
R ^b's each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms,
s and t represent integers that satisfy 1 ≦ s ≦ 3, 1 ≦ t ≦ 3, and s + t = 4. )
[2] The resin composition according to [1], wherein in the formula (1), R ^a represents an alkylene group having 4 or more carbon atoms.
[3] The resin composition according to [1] or [2], wherein in the formula (1), X represents an arylamino group.
[4] The resin composition according to any one of [1] to [3], in which the component (E) is represented by the following formula (2).

(In the formula (2), R ¹ and R ² each independently represent an aryl group which may have a substituent, and n represents an integer of 1 to 23.)
[5] The amount of the component (C) is 30% by mass or more and 90% by mass or less based on 100% by mass of the non-volatile component in the resin composition, according to any one of [1] to [4]. Resin composition.
[6] Any one of [1] to [5], wherein the amount of the component (E) is 0.1% by mass or more and 10% by mass or less based on 100% by mass of the nonvolatile component in the resin composition. The resin composition according to.
[7] The resin composition according to any one of [1] to [6], which is used for forming an insulating layer of a printed wiring board.
[8] A support,
A resin sheet, comprising a resin composition layer provided on a support and containing the resin composition according to any one of [1] to [7].
[9] The resin sheet according to [8], wherein the resin composition layer has a thickness of 15 μm or less.
[10] A printed wiring board including an insulating layer formed of the cured product of the resin composition according to any one of [1] to [7].
[11] A semiconductor device including the printed wiring board according to [10].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can suppress a haloing phenomenon and can obtain a thin insulating layer excellent in insulation; resin sheet provided with the resin composition layer containing said resin composition; And a printed wiring board and a semiconductor device containing a cured product of the above resin composition.

FIG. 1 is a cross-sectional view schematically showing an example of an insulating layer in which a first conductor layer and a second conductor layer are provided on both sides. FIG. 2 is a sectional view schematically showing an insulating layer formed of a cured product of a resin composition as an example together with an inner layer substrate. FIG. 3 is a plan view schematically showing a surface of an insulating layer formed of a cured product of a resin composition, which is opposite to the conductor layer. FIG. 4 is a cross-sectional view schematically showing an insulating layer after roughening treatment, which is formed of a cured product of a resin composition as an example, together with an inner layer substrate. FIG. 5 is a schematic sectional view of a printed wiring board as an example.

  Hereinafter, the present invention will be described in detail by showing embodiments and exemplifications. However, the present invention is not limited to the following embodiments and exemplifications, and may be implemented by being arbitrarily modified within the scope of the claims of the present invention and the scope of equivalents thereof.

[1. Outline of resin composition]
The resin composition according to one embodiment of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler having a specific surface area of 15 m ² / g or more, and (D) the following formula (1). The compound represented and the (E) phosphazene compound are included.

(X-R ^a ) _s Si (OR ^b ) _t (1)
(In formula (1),
X each independently represents an amino group which may have a substituent group, R ^a represents a divalent aliphatic hydrocarbon group optionally also be 4 or more carbon atoms have a substituent , R ^b each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, s and t are 1 ≦ s ≦ 3, 1 ≦ t ≦ 3, and , S + t = 4 is satisfied. )

  By using this resin composition, it is possible to obtain a thin insulating layer having excellent insulating properties and suppressing the haloing phenomenon.

[2. (A) component: epoxy resin]
Examples of the epoxy resin as the component (A) include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, Trisphenol 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 Examples thereof include resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins and the like. The epoxy resin (A) may be used alone or in combination of two or more.

  The resin composition preferably contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of remarkably obtaining the desired effects of the present invention, the ratio 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, and particularly preferably 70% by mass or more.

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

  As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable. Here, the “aromatic epoxy resin” means an epoxy resin having an aromatic ring in its molecule.

  Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. The alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin and epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy resin are preferable. A resin is more preferable, and a bisphenol A type epoxy resin is particularly preferable.

  Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D” and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “jER828EL”, “825” and “Epicoat” manufactured by Mitsubishi Chemical Corporation. 828EL "(bisphenol A type epoxy resin);" jER807 "and" 1750 "(bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co .;" jER152 "(phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co .; manufactured by Mitsubishi Chemical Co. "630", "630LSD" (glycidylamine type epoxy resin); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) made by Nippon Steel & Sumikin Chemical Co., Ltd .; "EX made by Nagase Chemtex Co., Ltd." -721 "(glycidyl ester type epoxy resin);" Celoxide 2021P "manufactured by Daicel Corporation (alicyclic epoxy resin having an ester skeleton);" PB-3600 "(epoxy resin having a butadiene structure) manufactured by Daicel Corporation; Nippon Steel "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Sumikin Chemical Co., Ltd. may be mentioned. These may be used alone or in combination of two or more.

  As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule is more preferable.

  As the 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, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and bixylenol type epoxy resin, biphenyl type epoxy resin, and bisphenol AF type epoxy resin is more preferable.

  Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; DIC "HP-7200HH", "HP-7200H", "EXA-7331", "EXA-7331-G3", "EXA-7331-G4", "EXA-7331-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) made by Nippon Steel & Sumikin Chemical Co., Ltd. "ESN485" (naphthol novolak) made by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin); "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000H", "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co .; YX8800 "(anthracene type epoxy resin);" PG-100 "and" CG-500 "manufactured by Osaka Gas Chemicals;" YL7760 "and" YX7760 "(bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; Mitsubishi Chemical "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical "jER1010" (solid bisphenol A type epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical (tetraphenylethane type epoxy resin) and the like. .. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the (A) epoxy resin, the quantity ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1:20 by mass ratio. , More preferably 1: 2 to 1:15, and particularly preferably 1: 5 to 1:13. When the amount ratio of the liquid epoxy resin and the solid epoxy resin is in such a range, the effects of improving the insulating property and suppressing the haloing phenomenon can be remarkably obtained. In addition, usually, when used in the form of a resin sheet, appropriate tackiness and sufficient flexibility are obtained, and handleability is improved. Furthermore, usually, a cured product having sufficient breaking strength can be obtained.

  The epoxy equivalent of the epoxy resin (A) is preferably 50 g / eq. ~ 5000 g / eq. , And more preferably 50 g / eq. ~ 3000 g / eq. , And more preferably 80 g / eq. ~ 2000 g / eq. , And even more preferably 110 g / eq. ~ 1000 g / eq. Is. When the epoxy equivalent is in this range, the cured product of the resin composition has a sufficient crosslink density, and an insulating layer having a small surface roughness can be obtained. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

  The weight average molecular weight (Mw) of the (A) epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. Is 400 to 1500.

  The weight average molecular weight of the resin can be measured as a polystyrene conversion value by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column, and chloroform as a mobile phase. And the like, the column temperature can be measured at 40 ° C., and can be calculated using a calibration curve of standard polystyrene.

  The amount of the epoxy resin (A) in the resin composition is preferably 5% by mass with respect to 100% by mass of the non-volatile components in the resin composition, from the viewpoint of obtaining an insulating layer having good mechanical strength and insulation reliability. As described above, the content is more preferably 10% by mass or more, and further preferably 15% by mass or more. The upper limit of the content of the epoxy resin is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass from the viewpoint of remarkably obtaining the effect of improving the insulating property and suppressing the haloing phenomenon. % Or less.

[3. (B) component: curing agent]
The resin composition contains (B) a curing agent. The curing agent (B) usually has a function of reacting with the epoxy resin (A) to cure the resin composition.

  Examples of the curing agent as the component (B) include active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, amine curing agents. , Acid anhydride type curing agents and the like. Further, the curing agent (B) 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 the active ester-based curing agent, two or more ester groups having high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are used. The compounds having are preferred. The active ester type curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..

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

  Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples thereof include benzenetriol, dicyclopentadiene type diphenol compound, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

  Preferred specific examples of the active ester-based curing agent include an active ester-based curing agent containing a dicyclopentadiene type diphenol structure, an active ester-based curing agent containing a naphthalene structure, and an active ester-based curing agent containing an acetylated product of phenol novolac, An active ester-based curing agent containing a benzoylated product of phenol novolac can be mentioned. Above all, an active ester-based curing agent containing a naphthalene structure and an active ester-based curing agent containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H" as active ester curing agents containing a dicyclopentadiene type diphenol structure. , "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC); active ester containing naphthalene structure. "EXB9416-70BK", "EXB-8150-65T" (manufactured by DIC) as a system hardener; "DC808" (manufactured by Mitsubishi Chemical) as an active ester hardener containing an acetylated product of phenol novolak; benzoyl of phenol novolak As an active ester-based curing agent containing a compound, "YLH1026" (manufactured by Mitsubishi Chemical Co.); As an active ester-based curing agent that is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co.); Examples of the ester-based curing agent include “YLH1026” (manufactured by Mitsubishi Chemical Corporation), “YLH1030” (manufactured by Mitsubishi Chemical Corporation), “YLH1048” (manufactured by Mitsubishi Chemical Corporation) and the like.

  As the phenol-based curing agent and the naphthol-based curing agent, those having a novolac structure are preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", and "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", "SN-" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 395 ";" TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "," EXB-9500 "; and the like manufactured by DIC.

  Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa High Polymer Co., Ltd., and "Pd" manufactured by Shikoku Chemicals Co., Ltd., "Fa" is mentioned.

  Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenyl propane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) A bifunctional cyanate resin such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and the like; prepolymers obtained by partially converting these cyanate resins into triazine. Specific examples of the cyanate ester-based curing agent include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), and “BA230” manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which a part or all of bisphenol A dicyanate is triazined into a trimer) and the like.

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

  Examples of the amine-based curing agent include curing agents having one or more amino groups in one molecule. Examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Can be mentioned. Of these, aromatic amines are preferable. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4′-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3 ′. -Diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, Bis (4- (3-aminophenoxy) phenyl) sulfone and the like can be mentioned. The amine-based curing agent may be a commercially available product, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard A-B", and "Kayahard AB" manufactured by Nippon Kayaku Co., Ltd. Kayahard A-S "," Epicure W "manufactured by Mitsubishi Chemical Corporation, and the like.

  Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride and hydrogenated methylnadic acid. Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride Mellitic acid, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenyl sulfone tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione, ethylene glycol bis (anhydrotrimellitate), and polymer type acid anhydrides such as a styrene-maleic acid resin in which styrene and maleic acid are copolymerized. Examples of commercially available acid anhydride curing agents include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

  Among the above, the (B) curing agent is preferably an active ester type curing agent, a phenol type curing agent and a carbodiimide type curing agent from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. , An active ester type curing agent and a phenol type curing agent are more preferable, and an active ester type curing agent is particularly preferable. When an active ester-based curing agent is used, the content of the active ester-based curing agent with respect to (B) 100% by weight of the curing agent is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more. It is preferably 98% by mass or less, more preferably 96% by mass or less, still more preferably 94% by mass or less.

  The amount of the (B) curing agent in the resin composition is preferably 100% by mass of the non-volatile component in the resin composition, from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1 mass% or more, preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less. is there.

  When the number of epoxy groups in the (A) epoxy resin is 1, the number of active groups in the (B) curing agent is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, and preferably Is 2 or less, more preferably 1.5 or less, and further preferably 1 or less. Here, "(A) the number of epoxy groups in the epoxy resin" is a value obtained by summing all the values obtained by dividing the mass of the non-volatile components of the (A) epoxy resin present in the resin composition by the epoxy equivalent. Further, "(B) the number of active groups of the curing agent" is a value obtained by summing all the values obtained by dividing the mass of the non-volatile components of the (B) curing agent present in the resin composition by the active group equivalent. When the number of active groups of the curing agent (B) when the number of epoxy groups of the epoxy resin (A) is 1 is within the above range, the effects of improving the insulating property and suppressing the haloing phenomenon can be remarkably obtained. In general, the heat resistance of the cured product of the resin composition is further improved.

[4. (C) component: inorganic filler]
The resin composition contains, as the component (C), an inorganic filler having a specific surface area of 15 m ² / g or more. With the cured product of the resin composition containing the inorganic filler (C), it is possible to obtain a thin insulating layer having excellent insulating properties and suppressing the haloing phenomenon. In addition, since the coefficient of thermal expansion of the cured product of the resin composition can be usually reduced by the inorganic filler (C), reflow warpage can be suppressed.

  An inorganic compound is used as the material of the inorganic filler (C). Examples of the material of the inorganic filler, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , Barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Further, spherical silica is preferable as the silica. The inorganic filler may be used alone or in combination of two or more.

The specific surface area of the inorganic filler (C) is usually 15 m ² / g or more, preferably 20 m ² / g or more, and particularly preferably 30 m ² / g or more. The upper limit is not particularly limited, but is 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 the inorganic filler is calculated according to the BET method by using a specific surface area measuring device (“Macsorb HM-1210” manufactured by Mountech Co., Ltd.) to adsorb nitrogen gas on the sample surface and using the BET multipoint method. It can be obtained. The specific surface area of the inorganic filler (C) may be changed by surface treatment with a surface treatment agent such as the component (D). In that case, the range of the specific surface area of the (C) inorganic filler usually represents the range of the specific surface area of the (C) inorganic filler in a state where the surface treatment is not performed. In general, the surface treatment agent can be removed from the (C) inorganic filler by firing at a suitable temperature. Therefore, when the surface-treated (C) inorganic filler is obtained as a sample, the surface area is usually not treated by measuring the specific surface area after firing the (C) inorganic filler. The specific surface area of the inorganic filler (C) can be measured.

  Further, even when the specific surface area of the inorganic filler (C) is changed by the surface treatment, the change is usually small. Therefore, the specific surface area of the surface-treated (C) inorganic filler can fall within the range of the specific surface area of the (C) inorganic filler in the state where the surface treatment is not performed.

  By using the inorganic filler (C) having a specific surface area within the above range, it is possible to obtain a thin insulating layer having excellent insulating properties and capable of suppressing the haloing phenomenon. Further, when the (C) inorganic filler having the specific surface area within the above range is used, the insulating layer can be usually thinned. Further, usually, it is possible to easily control the shape of the via hole and form a via hole having a good shape.

  Examples of the inorganic filler (C) having a large specific surface area as described above include “UFP-30” and “UFP-40” manufactured by Denki Kagaku Kogyo Co., Ltd.

  The average particle size of the inorganic filler (C) is preferably 5.0 μm or less, more preferably 0.8 μm or less, and particularly preferably 0.4 μm or less. By using the inorganic filler (C) having a small average particle diameter as described above, the effects of improving the insulating property and suppressing the haloing phenomenon can be remarkably obtained. Further, usually, the insulating layer can be thinned and a via hole having a good shape can be formed. The lower limit of the average particle size is not particularly limited, but is preferably 50 nm or more, 60 nm or more, or 70 nm or more.

  The average particle diameter of the inorganic filler (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering particle size distribution measuring device and setting the median size as the average particle size. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring device, "LA-960" manufactured by Horiba Ltd. can be used. When this laser diffraction / scattering particle size distribution measuring device is used, it is possible to measure with a flow cell method with the light source wavelengths used being blue and red.

  The amount of the inorganic filler (C) in the resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, with respect to 100% by mass of the nonvolatile component in the resin composition. Among them, 50% by mass or more is preferable, and 55% by mass or more is particularly preferable. When the amount of the inorganic filler (C) is within the above range, the effects of improving the insulating property of the insulating layer and suppressing the haloing phenomenon can be remarkably obtained. Further, usually, the dielectric loss tangent of the insulating layer can be lowered, and the thermal expansion coefficient of the insulating layer can be reduced. The upper limit of the amount of the inorganic filler (C) is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass from the viewpoint of increasing the mechanical strength of the insulating layer. % Or less.

[5. Component (D): Compound represented by Formula (1)]
The resin composition contains the compound represented by the formula (1) as the component (D). The cured product of the resin composition containing the component (D) makes it possible to obtain a thin insulating layer having excellent insulating properties and suppressing the haloing phenomenon.

(X-R ^a ) _s Si (OR ^b ) _t (1)

  In the formula (1), X's each independently represent an amino group which may have a substituent. The number of substituents that the amino group has is arbitrary and may be one or two. Therefore, X may be an unsubstituted amino group in which a hydrogen atom is not substituted, may be a primary amino group in which one hydrogen atom of the amino group is substituted, and two hydrogen atoms of the amino group may be substituted. It may be a substituted secondary amino group. The substituents of the secondary amino group may be the same or different. Among them, X is preferably a primary amino group in which one hydrogen atom of the amino group is substituted, from the viewpoint of remarkably obtaining the effect of improving the insulating property of the insulating layer and suppressing the haloing phenomenon.

  The substituent that may be contained in X is preferably a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and an aromatic hydrocarbon group is preferable. Among them, examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group, and a phenyl group is particularly preferable. Moreover, the hydrogen atom of the said hydrocarbon group may be substituted by the secondary substituent. Examples of the secondary substituent include a halogen atom, an aryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group and a nitro group. , A hydroxy group, a mercapto group, an oxo group, and the like. Among them, the hydrocarbon group is preferably an unsubstituted hydrocarbon group having no secondary substituent. The number of carbon atoms of the substituent that can be contained in X is preferably 1 or more, more preferably 6 or more, preferably 14 or less, more preferably 10 or less. By using such a substituent, the effects of improving the insulating property of the insulating layer and suppressing the haloing phenomenon can be remarkably obtained.

  Preferable examples of X in the formula (1) include alkylamino groups such as primary alkylamino group, secondary alkylamino group, and tertiary alkylamino group; arylamino groups such as phenylamino group and naphthylamino group. Etc. Among them, X is preferably an arylamino group, and particularly preferably a phenylamino group.

  When the compound represented by the formula (1) contains a plurality of X's in one molecule, those X's may be the same or different.

In the formula (1), R ^a's each independently represent a divalent aliphatic hydrocarbon group having 4 or more carbon atoms, which may have a substituent. The number of carbon atoms of the divalent aliphatic hydrocarbon group is usually 4 or more, preferably 5 or more, more preferably 6 or more, particularly preferably 7 or more, preferably 20 or less, more preferably 15 or less, particularly preferably Is 12 or less. Among them, among the carbon chains contained in the divalent aliphatic hydrocarbon, the carbon chain connecting the Si atom represented by the formula (1) and the N atom of the amino group of X (hereinafter referred to as “main chain”) Sometimes, the number of carbon atoms of) may fall within the above range. When R ^a has a divalent aliphatic hydrocarbon group having the number of carbon atoms in such a range, it is possible to obtain a thin insulating layer having excellent insulating properties and capable of suppressing the haloing phenomenon.

  The divalent aliphatic hydrocarbon group may have a cyclic structure or a chain structure. Further, the divalent aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group such as an alkylene group, or an unsaturated aliphatic hydrocarbon group such as an alkenylene group and an alkynylene group. Among them, the divalent aliphatic hydrocarbon group is preferably a chain saturated aliphatic hydrocarbon group, and particularly preferably an alkylene group.

  The alkylene group may be linear or branched, but a linear alkylene group is preferable. Preferred examples of the alkylene group include a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group and a dodecylene group.

  The alkenylene group may be linear or branched, but linear alkenylene groups are preferred. Preferable examples of the alkenylene group include butenylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, nonenylene group, decenylene group, undecenylene group and dodecenylene group.

  The alkynylene group may be linear or branched, but linear alkynylene groups are preferred. Preferable examples of the alkynylene group include butynylene group, pentynylene group, hexynylene group, heptynylene group, and octynylene group.

Examples of the substituent that the divalent aliphatic hydrocarbon group for R ^a may have include the same examples as the secondary substituent that X may include. However, R ^a is an unsubstituted divalent aliphatic hydrocarbon group having no substituent from the viewpoint of remarkably obtaining the effect of improving the insulating property of the insulating layer and suppressing the haloing phenomenon. Is preferred.

When the compound represented by the formula (1) contains ^a plurality of R ^{a in} one molecule, those R ^a may be the same or different.

In the formula (1), R ^b's each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the monovalent aliphatic hydrocarbon group for R ^b include a monovalent saturated aliphatic hydrocarbon group such as an alkyl group. Further, the aliphatic hydrocarbon group may have a cyclic structure or a chain structure. Furthermore, when the aliphatic hydrocarbon group has a chain structure, it may be linear or branched. The number of carbon atoms of R ^b is usually 1 to 3, preferably 1 to 2, and more preferably 1. Specific examples of the monovalent aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group and propyl group.

When the compound represented by formula (1) contains a plurality of groups R ^b in one molecule, those R ^b may be the same or different.

  In the formula (1), s and t represent integers satisfying 1 ≦ s ≦ 3, 1 ≦ t ≦ 3, and s + t = 4. Above all, s is preferably 1 to 2 and t is preferably 2 to 3 from the viewpoint of remarkably obtaining the effect of improving the insulating property and suppressing the haloing phenomenon.

  Examples of the compound represented by the formula (1) include unsubstituted aminotriacylsilane such as 8-aminooctyl-trimethoxysilane and 8-aminooctyl-triethoxysilane; N-phenyl-4-amino. Butyl-trimethoxysilane, N-phenyl-5-aminopentyl-trimethoxysilane, N-phenyl-6-aminohexyl-trimethoxysilane, N-phenyl-7-aminoheptyl-trimethoxysilane, N-phenyl-8 -Aminooctyl-trimethoxysilane, N-phenyl-9-aminononyl-trimethoxysilane, N-phenyl-10-aminodecyl-trimethoxysilane, N-phenyl-8-aminooctyl-triethoxysilane, N-naphthyl-8 -N-arylaminotrialkoxysilanes such as -aminooctyl-trimethoxysilane; N, N-diphenyl-8-aminooctyl-trimethoxysilane, such as N, N-diphenyl-8-aminooctyl-triethoxysilane, N, N-diarylaminotrialkoxysilane; and the like. Among them, N-arylaminotrialkoxysilane is preferable, and N-aryl-8-aminooctyl-trialkoxysilane is particularly preferable.

  As the component (D), one type may be used alone, or two or more types may be used in combination at any ratio.

  The molecular weight of the component (D) is preferably 193 or more, more preferably 270 or more, particularly preferably 300 or more, preferably 550 or less, more preferably 500 or less, more preferably 450 or less. When the molecular weight of the component (D) is within the above range, the effects of improving the insulating property and suppressing the haloing phenomenon can be remarkably obtained.

  In the resin composition, the component (D) may be separated from the inorganic filler as the component (C) and may be liberated in the resin component. Here, the resin component of the resin composition refers to a component excluding the inorganic filler from the nonvolatile components contained in the resin composition. However, the component (D) is preferably present on the surface of the inorganic filler (C) from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. Therefore, the inorganic filler (C) is preferably surface-treated with the component (D). Further, when the component (D) is present on the surface of the inorganic filler (C), the component (D) functions as a surface treatment agent, and thus the moisture resistance and dispersibility of the insulating layer can be usually enhanced.

  The amount of the component (D) in the resin composition is preferably 0 relative to 100% by mass of the non-volatile component in the resin composition from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. 0.1% by mass or more, more preferably 0.3% by mass or more, particularly preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less. Is.

  The amount of the component (D) in the resin composition is preferably 0. 0 with respect to 100 parts by mass of the inorganic filler (C) from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. 2 parts by mass or more, more preferably 0.3 parts by mass or more, particularly preferably 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, particularly preferably 3 parts by mass or less. is there. When the inorganic filler (C) is surface-treated with the component (D) in the above-mentioned amount, the effects of improving the insulating property and suppressing the haloing phenomenon can be remarkably obtained.

When the inorganic filler (C) is surface-treated with the component (D), the degree of surface treatment with the component (D) can be evaluated by the amount of carbon per unit surface area of the inorganic filler (C). it can. The amount of carbon per unit surface area of the inorganic filler (C) is preferably 0.02 mg / m ² or more, and 0.1 mg / m ² or more, from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. m ² or more is more preferable, 0.2 mg / m ² or more is further preferable, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. Further, when the carbon amount is at least the lower limit value of the above range, the dispersibility of the inorganic filler (C) can be usually improved, and when it is at most the upper limit value of the above range, the resin is usually resin. It is possible to suppress an increase in the melt viscosity of the varnish and the melt viscosity in the sheet form.

  The amount of carbon per unit surface area of the inorganic filler can be measured after cleaning the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of the component (D) per 1 m ² of surface area of the inorganic filler (C) is preferably 0.05 mg or more, more preferably 0.1 mg or more, particularly preferably 0.5 mg or more, preferably 500 mg or less, It is more preferably 100 mg or less, and particularly preferably 10 mg or less. The surface area of the (C) inorganic filler is obtained as the product of the specific surface area of the (C) inorganic filler and the mass of the (C) inorganic filler. When the amount of the component (D) per 1 m ² of surface area of the inorganic filler (C) is within the above range, the effects of improving the insulating property and suppressing the haloing phenomenon can be remarkably obtained.

[6. (E) component: phosphazene compound]
The resin composition contains a phosphazene compound as the component (E). With the cured product of the resin composition containing the (E) phosphazene compound, a thin insulating layer having excellent insulating properties and capable of suppressing the halo phenomenon can be obtained.

  The (E) phosphazene compound means a compound containing a structural unit represented by -P = N-. Examples of the phosphazene compound include a cyclophosphazene compound having a cyclic structure composed of a structural unit represented by -P = N-, a polyphosphazene compound having a chain structure composed of a structural unit represented by -P = N-, and the like. Is mentioned. As the phosphazene compound (E), one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  Among them, as the (E) phosphazene compound, a cyclophosphazene having a cyclic structure composed of a structural unit represented by -P = N- is used as the (E) phosphazene compound from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. Compounds are preferred. Furthermore, as the phosphazene compound (E), a phosphazene compound represented by the following formula (2) is particularly preferable.

(In the formula (2), R ¹ and R ² each independently represent an aryl group which may have a substituent, and n represents an integer of 1 to 23.)

In formula (2), R ¹ and R ² each independently represent an aryl group which may have a substituent. Preferably, R ¹ and R ² are each independently a hydroxy group, an alkyl group, an alkoxy group, a cyano group, a halogen atom, and -X ¹ -R ³ (X ¹ is a single bond,-(alkylene group). _{-, - O -, - S} -, - CO -, - SO 2 -, - NHCO -, - CONH -, - OCO-, or -COO- are shown, ^{R 3} is hydroxy group, an alkyl group, an alkoxy group , An aryl group which may have 1 to 3 substituents selected from the group consisting of a cyano group and a halogen atom), and 1 to 3 substituents selected from the group consisting of Represents an aryl group which may have.

The phosphazene compound (E) preferably does not contain a functional group capable of reacting with the epoxy resin (A) or the curing agent (B) from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. .. Examples of such a functional group include a hydroxy group and the like. Therefore, it is more preferable that R ¹ and R ² are each independently, an alkyl group, an alkoxy group, a cyano group, a halogen atom, and -X ¹ -R ⁴ (X ¹ is a single bond,-(alkylene group). _{-, - O -, - S} -, - CO -, - SO 2 -, - NHCO -, - CONH -, - OCO-, or -COO- are shown, ^{R 4} is an alkyl group, an alkoxy group, a cyano group And an aryl group which may have 1 to 3 substituents selected from the group consisting of halogen atoms.) And 1 to 3 substituents selected from the group consisting of The aryl group which may be shown is shown. More preferably, R ¹ and R ² are each independently an aryl group optionally having 1 to 3 substituents selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, and a halogen atom. Indicates. R ¹ and R ² are particularly preferably each independently an unsubstituted aryl group.

In one embodiment, preferably R ¹ is an unsubstituted aryl group, and R ² is each independently a hydroxy group, an alkyl group, an alkoxy group, a cyano group, a halogen atom, and —X ¹ —. It is an aryl group optionally having 1 to 3 substituents selected from the group consisting of groups represented by R ³ . More preferably, R ¹ is an unsubstituted aryl group, and R ² is each independently an alkyl group, an alkoxy group, a cyano group, a halogen atom, and a group represented by —X ¹ -R ^4. It is an aryl group optionally having 1 to 3 substituents selected from the group consisting of:

  In formula (2), the aryl group preferably has 6 to 14 carbon atoms, and more preferably has 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, and a phenyl group is preferable.

  In the formula (2), the alkyl group may be linear or branched. In formula (2), the alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group.

  In the formula (2), the number of carbon atoms of the alkoxy group is preferably 1-6, more preferably 1-3. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and a pentyloxy group.

In the formula (2), the alkylene group may be linear or branched. Further, in the formula (2), the number of carbon atoms of the alkylene group is preferably 1 to 6, and more preferably 1 to 3. As the alkylene group, _{e.g., -CH 2 -, - CH 2} -CH 2 -, - CH (CH 3) -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) - _{, -CH (CH 3) -CH 2} -, - C (CH 3) 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -, - _{CH 2 -CH (CH 3) -CH} 2 -, - CH (CH 3) -CH 2 -CH 2 -, - CH 2 -C (CH 3) 2 -, - C (CH 3) 2 -CH 2 - Etc.

  In the formula (2), n usually represents an integer of 1 to 23, preferably an integer of 1 to 13, more preferably an integer of 1 to 8, and further preferably 1 or 2. Particularly preferably, 1 is shown.

  Specific examples of the (E) phosphazene compound include compounds represented by the following formulas (2-1) to (2-8). In the following formulas (2-1) to (2-8), n is the same as above.

  As the phosphazene compound (E), a commercially available product may be used. For example, "SPH-100" (compound represented by the above formula (2-6)), "SPS-100" (compound represented by the above formula (2-1)), "SPB-" manufactured by Otsuka Chemical Co., Ltd. 100 "," SPE-100 ";" FP-100 "(compound represented by the above formula (2-1)) manufactured by Fushimi Pharmaceutical Co., Ltd.," FP-110 "," FP-300 "(the above formula ( 2-2)), "FP-390" (compound represented by the above formula (2-3)), "FP-400"; and the like.

  As the phosphazene compound (E), one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

  The amount of the (E) phosphazene compound in the resin composition is preferably 100% by mass of the non-volatile component in the resin composition from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. 0.1 mass% or more, more preferably 0.3 mass% or more, particularly preferably 0.5 mass% or more, preferably 10 mass% or less, more preferably 5 mass% or less, particularly preferably 3 mass% It is below.

  The amount of the (E) phosphazene compound in the resin composition is preferably 0 based on 100 parts by mass of the (C) inorganic filler from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, particularly preferably 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, particularly preferably 3 parts by mass or less. Is.

The amount of the (E) phosphazene compound per 1 m ² of surface area of the inorganic filler (C) is preferably 0.01 mg or more, more preferably 0.05 mg or more, particularly preferably 0.1 mg or more, and preferably 50 mg or less. , More preferably 10 mg or less, particularly preferably 2 mg or less. When the amount of the (E) phosphazene compound per 1 m ² of the surface area of the inorganic filler (C) is in the above range, the effects of improving the insulating property and suppressing the haloing phenomenon can be remarkably obtained.

[7. (F) component: curing accelerator]
The resin composition may further contain an optional component in combination with the above components. For example, the resin composition may include (F) a curing accelerator as an optional component.

  Examples of the curing accelerator (F) include a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, a guanidine curing accelerator, and a metal curing accelerator. Of these, 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.

  Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1, Examples thereof include 8-diazabicyclo (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 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'-undecyl Imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins are mentioned, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

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

  Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-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 Examples thereof include allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide, and dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene.

  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, and zinc (II) acetylacetonate. And the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

  When the (F) curing accelerator is used, the amount of the (F) curing accelerator in the resin composition is set in the resin composition from the viewpoint that the effect of improving the insulating property and suppressing the haloing phenomenon can be remarkably obtained. With respect to 100% by mass of the non-volatile components, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably Is 2% by mass or less, more preferably 1.5% by mass or less.

[8. (G) component: thermoplastic resin]
The resin composition may contain (G) a thermoplastic resin as an optional component.

  Examples of the thermoplastic resin as the component (G) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene ether resin. , Polycarbonate resin, polyether ether ketone resin, polyester resin and the like. Among them, the phenoxy resin is preferable from the viewpoint of remarkably obtaining the effect of improving the insulating property and suppressing the haloing phenomenon, and from the viewpoint of obtaining the insulating layer having a small surface roughness and particularly excellent adhesion to the conductor layer. The thermoplastic resins may be used alone or in combination of two or more.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene. Phenoxy resins having one or more types of skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton are mentioned. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical Corporation "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (phenoxy resin containing bisphenolacetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation. "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482"; and the like.

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

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

  Specific examples of the polyamide-imide resin include “Vylomax HR11NN” and “Vylomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical.

  Specific examples of the polyether sulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd. and the like.

  Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company.

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

  (G) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. It is particularly preferably 20,000 or more, preferably 70,000 or less, more preferably 60,000 or less, particularly preferably 50,000 or less.

  In the case of using the (G) thermoplastic resin, the amount of the (G) thermoplastic resin in the resin composition is not limited to that in the resin composition from the viewpoint of remarkably obtaining the effects of improving the insulating property and suppressing the haloing phenomenon. With respect to 100% by mass of the non-volatile component, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 15% by mass or less, more preferably 12 It is not more than 10% by mass, more preferably not more than 10% by mass.

[9. (H) component: other arbitrary component]
The resin composition may further contain an optional additive as an optional component in addition to the above-mentioned components. Examples of such additives include organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; flame retardants, thickeners, defoamers, leveling agents, adhesion promoters, Resin additives such as colorants; and the like. These additives may be used alone or in combination of two or more.

[10. Method for producing resin composition]
The above-mentioned resin composition can be produced, for example, by stirring the blended components using a stirring device such as a rotary mixer and uniformly dispersing them.

[11. Characteristics of resin composition]
When the insulating layer is formed by the cured product of the resin composition described above, the insulating layer has excellent insulating properties and can suppress the haloing phenomenon. Further, these effects can be exhibited even if the insulating layer is thin. Therefore, according to the resin composition described above, it is possible to obtain a thin insulating layer having excellent insulating properties and suppressing the haloing phenomenon.

Regarding the excellent insulating property, specifically, when the insulating layer is formed of a cured product of the resin composition, the resistance of the insulating layer can be increased. In one embodiment, when the surface of the insulating layer obtained by heating the resin composition at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes to cure is subjected to a roughening treatment, the insulating layer is high. The insulation resistance value can be indicated. For example, the insulation resistance value of the insulating layer having a thickness of 4.0 μm or more and 5.0 μm or less between the conductor layers is preferably 1.0 × 10 ⁷ Ω or more, more preferably 1.0 × 10 ⁸ Ω or more, It is more preferably 1.0 × 10 ⁹ Ω or more, and particularly preferably 1.0 × 10 ¹⁰ Ω or more. The insulation resistance value can be measured by the method described in Examples described later (see [I. Measurement of thickness of insulating layer between conductor layers and insulation reliability of insulating layer]).

  FIG. 1 is a cross-sectional view schematically showing an example of an insulating layer 3 provided with a first conductor layer 1 and a second conductor layer 2 on both sides. As shown in FIG. 1, the “thickness of the insulating layer between the conductor layers” means the conductor layers provided on both sides of the insulating layer 3 (the first conductor layer 1 and the second conductor layer 2 in FIG. 1). Represents the thickness t1 of the insulating layer 3 between the parentheses. That is, the “thickness of the insulating layer between the conductor layers” represents the thickness t1 of the insulating layer 3 between the main surface 11 of the first conductor layer 1 and the main surface 21 of the second conductor layer 2. Here, the first conductor layer 1 and the second conductor layer 2 are conductor layers adjacent to each other with the insulating layer 3 in between, and the main surface 11 and the main surface 21 face each other.

  Regarding the point that the haloing phenomenon can be suppressed, specifically, when the via hole is formed in the insulating layer formed by the cured product of the resin composition and the roughening treatment is performed, the haloing phenomenon can be suppressed. .. Hereinafter, the suppression of the haloing phenomenon will be described in more detail with reference to the drawings.

  FIG. 2 is a sectional view schematically showing an insulating layer 100 formed of a cured product of a resin composition as an example together with an inner layer substrate 200. FIG. 2 shows a cross section of insulating layer 100 cut along a plane that passes through center 120C of bottom 120 of via hole 110 and is parallel to the thickness direction of insulating layer 100.

  As shown in FIG. 2, the insulating layer 100 according to this example is formed of a cured product of a resin composition on the inner layer substrate 200 including the conductor layer 210. A via hole 110 is formed in the insulating layer 100. The via hole 110 is generally formed in a forward tapered shape having a larger diameter as it approaches the surface 100U of the insulating layer 100 on the opposite side to the conductor layer 210 and a smaller diameter as it approaches 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 usually formed by irradiating the surface 100U 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 a “via bottom” and denoted by reference numeral 120. Further, the opening formed on the side of the via hole 110 opposite to the conductor layer 210 is appropriately referred to as a “via top” and designated by reference numeral 130. Normally, the via bottom 120 and the via top 130 are formed to have a circular plan shape when viewed in the thickness direction of the insulating layer 100, but may have an elliptical shape.

FIG. 3 is a plan view schematically showing a surface 100U of the insulating layer 100 formed of a cured product of a resin composition, which is opposite to the conductor layer 210 (not shown in FIG. 3). ..
As shown in FIG. 3, when the insulating layer 100 having the via hole 110 is viewed, a discolored portion 140 in which the insulating layer 100 is discolored may be observed around the via hole 110. The discolored portion 140 can be formed when the via hole 110 is formed, and is usually formed continuously from the via hole 110. In many cases, the discolored portion 140 is a whitened portion.

FIG. 4 is a cross-sectional view schematically showing an insulating layer 100 after a roughening treatment, which is formed of a cured product of a resin composition, together with an inner layer substrate 200. FIG. 4 shows a cross section of insulating layer 100 taken along a plane that passes through center 120C of via bottom 120 of via hole 110 and is parallel to the thickness direction of insulating layer 100.
As shown in FIG. 4, when the insulating layer 100 in which the via hole 110 is formed is roughened, a haloing phenomenon occurs, the insulating layer 100 of the discolored portion 140 is separated from the conductor layer 210, and the edge of the via bottom 120 is removed. A continuous gap 160 may be formed from 150. The gap 160 is usually formed by eroding the discolored portion 140 during the roughening process.

  By using the resin composition described above, the haloing phenomenon can be suppressed. Therefore, peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, and the size of the gap 160 can be reduced.

  The edge 150 of the via bottom 120 corresponds to the inner peripheral edge of the gap 160. Therefore, the distance Wb from the edge 150 of the via bottom 120 to the outer peripheral side end of the gap 160 (that is, the end farther from the center 120C of the via bottom 120) 170 is the size of the gap 160 in the in-plane direction. Equivalent to. Here, the in-plane direction means 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 halo distance Wb from the edge 150 of the via bottom 120 of the via hole 110. The degree of suppression of the halo phenomenon can be evaluated by the halo distance Wb from the edge 150 of the via bottom 120. Specifically, it can be evaluated that the haloing phenomenon was effectively suppressed as the haloing distance Wb from the edge 150 of the via bottom 120 was smaller.

In one embodiment, the resin composition is heated at 130 ° C. for 30 minutes, and then heated at 170 ° C. for 30 minutes to be cured, and then the insulating layer 100 having a thickness of 10 μm is applied to a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0. 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 2 mJ / shot, the number of shots 2 and the burst mode (10 kHz). Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then in the roughening solution at 80 ° C. for 20 minutes, then in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. When the resin composition described above is used, the haloing distance Wb of the via hole 110 of the insulating layer 100 thus obtained from the edge 150 of the via bottom 120 is preferably 5 μm or less, more preferably 4 μm or less, and further preferably It can be 3 μm or less, particularly preferably 2 μm or less.

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

  Further, according to the study by the present inventors, it is generally found that the larger the diameter of the via hole 110 is, the larger the size of the color change portion 140 is, and thus the larger the size of the gap portion 160 is. There is. 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 with respect to the bottom radius Lb / 2 of the via hole 110. Here, the bottom radius Lb / 2 of the via hole 110 means the radius of the via bottom 120 of the via hole 110, and usually represents half the bottom diameter Lb of the via hole 110. The bottom diameter Lb of the via hole 110 means the diameter of the via bottom 120 of the via hole 110. Further, the haloing ratio Hb with respect 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 can be suppressed.

In one embodiment, the resin composition is heated at 130 ° C. for 30 minutes, and then heated at 170 ° C. for 30 minutes to be cured, and then the insulating layer 100 having a thickness of 10 μm is applied to a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0. 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 2 mJ / shot, the number of shots 2 and the burst mode (10 kHz). Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then in the roughening solution at 80 ° C. for 20 minutes, then in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. When the resin composition described above is used, the haloing ratio Hb of the insulating layer 100 thus obtained to the bottom radius Lb / 2 of the via hole 110 is preferably 50% or less, more preferably 40% or less, and further preferably Can be 30% or less, particularly preferably 20% or less.

  The haloing ratio Hb with respect 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.

  The present inventors presume the mechanism by which the excellent effects are obtained as described above as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

  First, the insulating property will be described. In the resin composition and the insulating layer containing the inorganic filler, generally, stress is likely to be concentrated on the interface between the inorganic filler and the resin component. In the method for manufacturing a printed wiring board, in the step of curing the resin composition, the step of forming a via hole in the insulating layer, and the step of forming a conductor layer on the insulating layer, stress is applied to the resin composition and the insulating layer. It is easy to occur. Further, if the printed wiring board is placed in an environment of high temperature or high humidity after the production of the printed wiring board, this may cause stress in the insulating layer. Therefore, conventionally, stress could be concentrated on the interface between the inorganic filler and the resin component, causing peeling at the interface, and the inorganic filler could be detached. If the inorganic filler is detached, holes may be formed in the insulating layer as traces of detachment. When this hole penetrates the insulating layer, it is considered that conduction through the hole is possible and the insulating property of the insulating layer is deteriorated.

On the other hand, the above-mentioned resin composition contains the component (D) and the phosphazene compound (E). Since part or all of the component (D) can be present on the surface of the inorganic filler (C), it can be present at the interface between the inorganic filler (C) and the resin component. Further, the component (D) has a divalent aliphatic hydrocarbon group as represented by R ^a in the formula (1). As can be seen from the large number of carbon atoms, this aliphatic hydrocarbon group has a large range of free movement and is flexible. Therefore, the component (D) can absorb stress at the interface between the inorganic filler (C) and the resin component.

  Furthermore, a part or all of the (E) phosphazene compound may be free from the crosslinked structure formed by the bond between the (A) epoxy resin and the (B) curing agent. Therefore, since the position of the (E) phosphazene compound can be changed in the resin component so as to relieve the stress, the stress can also be absorbed by the (E) phosphazene compound.

  Then, since the stress can be effectively absorbed by the combination of the component (D) and the phosphazene compound (E), the desorption of the inorganic filler (C) due to the stress can be suppressed. Further, the inorganic filler (C) having a large specific surface area generally has a small particle size. Therefore, even if the inorganic filler (C) is detached, it is difficult to form a large hole penetrating the insulating layer. Therefore, by using the resin composition described above, an insulating layer having excellent insulating properties can be realized.

  Next, suppression of the haloing phenomenon will be described. Normally, when forming a via hole, energy such as heat and light is applied to the portion of the insulating layer where the via hole is to be formed. A part of the energy applied at this time is transmitted to the periphery of the portion where the via hole is to be formed, and stress may be generated. If such an stress causes the interface between the inorganic filler and the resin component to separate and form a gap, liquids such as a swelling liquid and a roughening liquid easily enter the gap and promote erosion of the insulating layer. Can be done. Then, as the erosion of the insulating layer progresses, a haloing phenomenon occurs at the eroded portion, and the insulating layer may be separated from the conductor layer.

  On the other hand, the resin composition described above can effectively absorb stress by the combination of the component (D) and the phosphazene compound (E) as described above. Therefore, (C) the separation of the interface between the inorganic filler and the resin component can be suppressed, so that the erosion of the insulating layer can be suppressed. In particular, since the inorganic filler (C) has a large specific surface area, the above-mentioned action capable of suppressing the peeling of the interface between the inorganic filler (C) and the resin component is effective in suppressing the erosion of the insulating layer. Therefore, the haloing phenomenon can be suppressed by using the resin composition described above.

  In particular, according to the study by the present inventors, the above-mentioned action capable of suppressing the peeling of the interface between the inorganic filler and the resin component (C) is more effective than using the component (D) and the phosphazene compound (E) separately. Also, it has been found that the combined use of the component (D) and the phosphazene compound (E) is more remarkable.

  As shown in FIG. 4, when the above-mentioned resin composition is used, it is usually possible to easily control the shape of the via hole 110. Therefore, the shape of the via hole 110 can be improved. The good shape of the via hole 110 means that the taper rate Lb / Lt (%) obtained by dividing the bottom diameter Lb of the via hole 110 by the top diameter Lt is close to 100%. The top diameter Lt of the via hole 110 means the diameter of the via top 130 of the via hole 110. When the planar shapes of the via bottom 120 and the via top 130 are elliptical, the bottom diameter Lb and the top diameter Lt of the via bottom 120 and the via top 130 respectively represent the major axis of the elliptical shape.

In one embodiment, the resin composition is heated at 130 ° C. for 30 minutes, and then heated at 170 ° C. for 30 minutes to be cured, and then the insulating layer 100 having a thickness of 10 μm is applied to a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0. 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 2 mJ / shot, the number of shots 2 and the burst mode (10 kHz). Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then in the roughening solution at 80 ° C. for 20 minutes, then in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. When the resin composition described above is used, the taper rate Lb / Lt of the via hole 110 of the insulating layer 100 thus obtained is preferably 60% to 100%, more preferably 70% to 100%, and particularly preferably. It can be 80% 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, regarding the bottom diameter Lb and the top diameter Lt of the via hole 110, a cross section that is parallel to the thickness direction of the insulating layer 100 and that passes through the center 120C of the via bottom 120 appears using FIB (focused ion beam). After shaving, the cross section can be measured by observing it with an electron microscope.

  By using the resin composition described above, it is possible to usually suppress the formation of the discolored portion 140 when the via hole 110 is formed. Therefore, as shown in FIG. 3, the size of the color changing portion 140 can be reduced, and ideally the color changing portion 140 can be eliminated. The size of the discolored portion 140 can be evaluated by the halo 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 inner peripheral edge of the discolored portion 140. The halo 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 portion 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 is, the more effectively the formation of the discolored portion 140 can be suppressed.

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

  A plated conductor layer can be formed on the insulating layer formed of the cured product of the resin composition described above. In this case, usually, the peel strength between the insulating layer and the plated conductor layer can be increased. In one embodiment, the resin composition is heated at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes to cure. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then in the roughening solution at 80 ° C. for 20 minutes, then in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. By using the resin composition described above, the peel strength between the insulating layer thus obtained and the plated conductor layer formed on the surface can be increased. The specific peel strength can be, for example, preferably 0.30 kgf / cm or more, more preferably 0.40 kgf / cm or more, and still more preferably 0.45 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but may be 5 kgf / cm or less. The evaluation of the peel strength can be performed according to the method described in Examples (see [Measurement of peeling strength (peel strength) of plated conductor layer]) described later.

[12. Applications of resin composition]
The resin composition described above can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). Above all, the resin composition described above can be more preferably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board). Further, the resin composition described above is a resin composition for forming a conductor layer (including a rewiring layer) on the insulating layer (a resin composition for forming the conductor layer). It may be used as a resin composition for forming).

  In particular, from the viewpoint of effectively utilizing the advantage that the haloing phenomenon can be suppressed, the above-mentioned resin composition is a resin composition for forming an insulating layer having a via hole (a resin composition for forming an insulating layer having a via hole). In particular, it is particularly preferable as a resin composition for forming an insulating layer having a via hole having a top diameter of 35 μm or less.

  Furthermore, from the viewpoint of effectively utilizing the advantage that the insulating property can be improved and the haloing phenomenon can be suppressed even with a thin insulating layer, the resin composition described above is a resin for forming a thin insulating layer. It is preferably used as a composition, for example, suitable as a resin composition layer for forming an insulating layer having a thickness of 15 μm or less.

[13. Resin sheet]
A resin sheet according to one embodiment of the present invention includes a support and a resin composition layer provided on the support and containing the resin composition described above.

  The thickness of the resin composition layer is preferably 15 μm or less, more preferably 15 μm or less, from the viewpoint of making the printed wiring board thinner, and from the viewpoint of being able to provide an insulating layer excellent in insulation and suppressing haloing even if it is thin. Is 14 μm or less, more preferably 12 μm or less, and particularly preferably 10 μm or less. The lower limit of the thickness of the resin composition layer is arbitrary, and can be, for example, 1 μm or more and 3 μm or more.

  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, the plastic material may be, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) or polyethylene naphthalate (hereinafter sometimes referred to as “PEN”). .) Etc., polyesters, polycarbonates (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylates (hereinafter sometimes referred to as “PMMA”) acrylic polymers, cyclic polyolefins, triacetyl cellulose (hereinafter abbreviated as “PMMA”). "TAC" may be abbreviated), polyether sulfide (hereinafter abbreviated as "PES"), polyetherketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper 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) is used. You may use.

  The support may be subjected to a matting treatment, a corona treatment, an antistatic treatment or the like on its surface to be joined to the resin composition layer.

  Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used in the release layer of the support with release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used, for example, “SK-1” 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, "Unipeal" manufactured by Unitika Ltd., and the like.

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

  The resin sheet may include any layer other than the support and the resin composition layer, if necessary. Examples of such an optional layer include a protective film conforming to the support, which is provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By the protective film, it is possible to suppress the adhesion of dust or the like to the surface of the resin composition layer and the scratches.

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

  Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic acid ester 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 solvent may be used alone or in combination of two or more.

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

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

[14. Printed wiring board]
A printed wiring board according to an embodiment of the present invention includes an insulating layer formed of a cured product of the above resin composition. Even if this insulating layer is thin, it can suppress the halo phenomenon and has a good insulating property. Therefore, according to this printed wiring board, it is possible to reduce the thickness of the printed wiring board while suppressing the deterioration of the performance due to the haloing phenomenon or the insulation failure.

  A via hole may be formed in the insulating layer of the printed wiring board. The via hole is usually provided for conducting the conductor layers provided on both sides of the insulating layer having the via hole. Therefore, the printed wiring board may include the first conductor layer, the second conductor layer, and the 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 conducted through the via hole.

  Hereinafter, an example of a preferable printed wiring board will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view of the printed wiring board 300 as an example. FIG. 5 shows a cross section of printed wiring board 300 cut along a plane that passes through center 120C of via bottom 120 of via hole 110 and is parallel to the thickness direction of insulating layer 100. In addition, in FIG. 5, parts corresponding to the elements described in FIGS. 2 to 4 are denoted by the same reference numerals as those used in FIGS. 2 to 4.

  As shown in FIG. 5, the printed wiring board 300 according to the present example has a first conductor layer 210, a second conductor layer 220, and a space between the first conductor layer 210 and the second conductor layer 220. The formed insulating layer 100 is included. A via hole 110 is formed in the insulating layer 100. Further, the second conductor layer 220 is usually provided after the via hole 110 is formed. Therefore, the second conductor layer 220 is usually formed not only in the surface 100U 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 this via hole 110. is doing.

  The thickness T between the conductor layers of the insulating layer 100 included in the printed wiring board 300 is preferably 15 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less. The thickness T may be particularly preferably 6.0 μm or less, 5.5 μm or less, 5.0 μm or less. When the printed wiring board 300 has such a thin insulating layer 100, the printed wiring board 300 itself can be made thin. The lower limit of the thickness T 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 insulating performance of the insulating layer 100. Here, the thickness T between the conductor layers 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 corresponds to the thickness t1 in FIG. This thickness T usually corresponds to the depth of the via hole 110.

  In addition, the thickness of the insulating layer 100 (corresponding to the thickness t2 in FIG. 1) in a portion other than between the first conductor layer 210 and the second conductor layer 220 is arbitrary. This thickness can be preferably 15 μm or less, more preferably 13 μm or less, still more preferably 10 μm or less, and preferably 1 μm or more, more preferably 1.5 μm or more, still more preferably 2 μm or more.

  The top diameter Lt of the via hole 110 formed in the insulating layer 100 included in the printed wiring board 300 is preferably 35 μm or less, more preferably 33 μm or less, and further preferably 32 μm or less. When the printed wiring board 300 includes the insulating layer 100 having the via hole 110 having the small top diameter Lt as described above, miniaturization of the wiring including the first conductor layer 210 and the second conductor layer 220 can be promoted. 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 taper rate Lb / Lt (%) of the via hole 110 formed in the insulating layer 100 included in the printed wiring board 300 is preferably 60% to 100%, more preferably 70% to 100%, and particularly preferably 80% to 100%. Can be%. When the printed wiring board 300 is provided with the insulating layer 100 having the good shape via hole 110 having the high taper rate Lb / Lt as described above, conduction between the first conductor layer 210 and the second conductor layer 220 is achieved. The reliability can be effectively increased.

  The haloing distance Wb of the via hole 110 formed in the insulating layer 100 included in the printed wiring board 300 from the edge 150 of the via bottom 120 is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less, and particularly preferably 2 μm. It is below. In the printed wiring board 300, when the separation of the insulating layer 100 from the first conductor layer 210 is small as represented by the halo distance Wb, the first conductor layer 210 and the second conductor layer 220 are separated from each other. The reliability of conduction between the two can be effectively increased.

  The haloing ratio Hb of the via hole 110 formed in the insulating layer 100 included in the printed wiring board 300 to the bottom radius Lb / 2 is preferably 50% or less, more preferably 40% or less, further preferably 30% or less, and particularly preferably. Is 20% or less. In the printed wiring board 300, when the separation of the insulating layer 100 from the first conductor layer 210 is small as indicated by the haloing ratio Hb, the first conductor layer 210 and the second conductor layer 220 are separated from each other. The reliability of conduction between the two can be effectively increased. The lower limit of the haloing ratio Hb with respect to the bottom radius Lb / 2 is ideally zero, but is usually 5% or more.

  The number of via holes 110 formed in the insulating layer 100 included in the printed wiring board 300 may be one or two or more.

  The printed wiring board 300 according to the above example can be realized by forming the insulating layer 100 from a cured product of the resin composition described above. 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, and preferably circular.

There is no limitation on the manufacturing method of the printed wiring board. The printed wiring board can be manufactured, for example, by using a resin sheet and performing a manufacturing method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer is bonded to the inner layer substrate.
(II) A step of thermosetting the resin composition layer to form an insulating layer.

  The “inner layer substrate” used in the step (I) is a member that becomes a substrate of a printed wiring board. Examples of the inner layer substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. 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 this conductor layer. This conductor layer may be patterned in order to function as a circuit, for example. The 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 "inner layer circuit board". In addition, an intermediate product in which an insulating layer and / or a conductor layer is to be formed when manufacturing a printed wiring board is also included in the “inner layer substrate”. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

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

  The inner layer substrate and the resin sheet may be laminated by, for example, a vacuum laminating 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. It is in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

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

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

  After the step (I), the step (II) is performed. In the step (II), the resin composition layer is thermoset to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions adopted when forming the insulating layer of the printed wiring board may be arbitrarily used.

  The thermosetting conditions for the resin composition layer may vary depending on the type of resin composition and the like. The curing temperature may be preferably 120 ° C to 240 ° C, more preferably 150 ° C to 220 ° C, and further preferably 170 ° C to 200 ° C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 90 minutes.

  Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C or higher and lower than 150 ° C (preferably 60 ° C or higher and 140 ° C or lower, more preferably 70 ° C or higher and 130 ° C or lower). May be preheated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, further preferably 15 minutes to 100 minutes).

The method for manufacturing a printed wiring board may further include the following step (III), step (IV) and step (V).
(III) A step of forming a via hole in the insulating layer.
(IV) A step of subjecting the insulating layer to a roughening treatment.
(V) A step of forming a conductor layer.

  When the support is removed after the step (II), the support may be removed between the step (II) and the step (III), the step (III) and the step (IV), or the step (II). It may be carried out at any point between IV) and step (V). Above all, it is preferable to remove the support after the step (III) of forming the via hole in the insulating layer, from the viewpoint of further suppressing the generation of the gouged portion. For example, if the support is peeled off after forming a via hole in the insulating layer by irradiation with laser light, a via hole having a good shape can be easily formed.

  In step (III), a via hole is formed in the insulating layer. Examples of the method for forming the via hole include laser light irradiation, etching, and mechanical drilling. Above all, irradiation of laser light is preferable from the viewpoint of effectively utilizing the effect of suppressing the haloing phenomenon, because the haloing phenomenon generally occurs easily.

This laser light irradiation 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. Examples of the laser processing machine that can be used include CO ₂ laser processing machine “LC-2k212 / 2C” manufactured by Via Mechanics, 605GTWIII (−P) manufactured by Mitsubishi Electric Corporation, laser processing machine manufactured by Matsushita Welding Systems, and the like. Is mentioned.

  In step (IV), the insulating layer is roughened. In the step (IV), for example, swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent as a roughening liquid, and neutralization treatment with a neutralizing liquid are performed in this order to roughen the insulating layer. You can

  The swelling liquid is not particularly limited, but examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. As the alkaline solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Further, the swelling liquid may be used alone or in combination of two or more kinds at an arbitrary ratio. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes.

  The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. In addition, one kind of the oxidizing agent may be used alone, or two or more kinds thereof may be used in combination at an arbitrary ratio. The roughening treatment with an oxidizing agent such as an alkaline permanganate 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. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP”, “Concentrate Compact P”, and “Dosing Solution Securigans P” manufactured by Atotech Japan. ..

  The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. The neutralizing solution may be used alone or in combination of two or more kinds at an arbitrary ratio. The treatment with the neutralizing solution can be performed by immersing the treated surface, which has been roughened with an oxidizing agent, in the neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the object roughened with the oxidizing agent in a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes.

  Step (V) is a step of forming a conductor layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include a layer formed of an alloy of two or more kinds of metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or a nickel-chromium alloy, copper from the viewpoints of versatility of forming a conductor layer, cost, easiness of patterning and the like. An alloy layer of nickel alloy or copper / titanium alloy is preferable. Further, 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 a multi-layer structure including two or more single metal layers or alloy layers made of different kinds 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 depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

  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 semi-additive method is preferably used from the viewpoint of ease of production.

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

  Moreover, you may manufacture a multilayer printed wiring board by repeating formation of the insulating layer and conductor layer by process (I) -process (V) as needed.

[15. Semiconductor device]
A semiconductor device according to one embodiment of the present invention includes the printed wiring board described above. This semiconductor device can be manufactured using a printed wiring board.

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

  The semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conducting portion" is a "portion for transmitting an electric signal in the printed wiring board", and the location may be a surface or an embedded portion. Further, the semiconductor chip can optionally use an electric circuit element made of a semiconductor.

  The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Examples of the mounting method include a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, and a non-conductive film (NCF) mounting method. Method, etc. Here, the "mounting method using a bump-free 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 wiring on the printed wiring board". Is.

  Hereinafter, the present invention will be specifically described with reference to 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 “mass%”, respectively, unless otherwise specified. The operations described below were performed in an environment of normal temperature and normal pressure unless otherwise specified.

[Treatment filler 1]
Spherical silica (“UFP-30” manufactured by Denka Co., specific surface area 30.7 m ² / g, average particle size 0.3 μm) was used as N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight The particles surface-treated in 325.2) were prepared as the treatment filler 1. The treatment filler 1 is particles obtained by treating 100 parts of spherical silica with 3 parts of N-phenyl-8-aminooctyl-trimethoxysilane.

[Treatment filler 2]
Spherical silica (Denka “UFP-30”, specific surface area 30.7 m ² / g, average particle size 0.3 μm) was mixed with N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. “KBM573”). The particles surface-treated with (1) were prepared as the treatment filler 2. The treatment filler 2 is particles obtained by treating 100 parts of spherical silica with 2 parts of N-phenyl-3-aminopropyltrimethoxysilane.

[Treatment filler 3]
Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., specific surface area 5.9 m ² / g, average particle size 0.5 μm) was mixed with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., Particles surface-treated with a molecular weight of 325.2) were prepared as the treatment filler 3. The treatment filler 3 is particles obtained by treating 100 parts of spherical silica with 1 part of N-phenyl-8-aminooctyl-trimethoxysilane.

[Measurement method of average particle size of inorganic filler]
The average particle size of the inorganic filler was measured by the following method.
100 mg of the above inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves for 10 minutes. Using a laser diffraction type particle size distribution measuring device (“LA-960” manufactured by Horiba Ltd.), the light source wavelengths used were blue and red, and the particle size distribution of the inorganic filler was measured on a volume basis by a flow cell method. From the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median size.

[Method of measuring specific surface area of inorganic filler]
The specific surface area of the inorganic filler was measured by the following method.
Using a BET fully automatic specific surface area measuring device (“Macsorb HM-1210” manufactured by Mountech Co., Ltd.), nitrogen gas was adsorbed to the inorganic filler, and the specific surface area was calculated using the BET multipoint method.

[Example 1: Preparation of resin composition 1]
5 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Co., epoxy equivalent about 180), 20 parts of bisphenol AF type epoxy resin ("YX7760" manufactured by Mitsubishi Chemical Co., epoxy equivalent about 238), bixylenol type epoxy resin ( Mitsubishi Chemical's "YX4000H", epoxy equivalent about 190) 25 parts, phosphazene resin (Otsuka Chemical's "SPS-100") 3 parts, phenoxy resin (Mitsubishi Chemical's "YX7553BH30", solid content 30 mass% MEK. And 1 part of a cyclohexanone solution of 10 parts) were dissolved in 60 parts of MEK by heating with stirring.

After cooling to room temperature, 70 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC, an active group equivalent of about 223, a toluene solution having a solid content of 65 mass%), a phenol-based curing agent (manufactured by DIC) "LA-3018-50P", active group equivalent weight 151, 2-methoxypropanol solution having 50% solid content) 6 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having 5% solid content) 6 parts, treated filler 1 (N-phenyl-8-aminooctyl-trimethoxysilane (Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) spherical silica surface-treated (Denka "UFP-30", ratio 180 parts of a surface area of 30.7 m ² / g and an average particle size of 0.3 μm) were mixed and uniformly dispersed by a high-speed rotating mixer. Then, it filtered with the cartridge filter ("SHP020" by ROKITECHNO), and resin composition 1 was produced.

[Example 2: Preparation of resin composition 2]
In Example 1, the bisphenol AF type epoxy resin (“YX7760” manufactured by Mitsubishi Chemical Co., epoxy equivalent: 238) was changed to a biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., epoxy equivalent: 271). Also, the phosphazene resin (“SPS-100” manufactured by Otsuka Chemical Co., Ltd.) was changed to a phosphazene resin (“SPH-100” manufactured by Otsuka Chemical Co., Ltd.). Further, the amount of the phenol-based curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151, solid content 50% 2-methoxypropanol solution) was changed from 6 parts to 3 parts. Further, 6 parts of a carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Inc., an active group equivalent of about 216, a toluene solution having a solid content of 50% by mass) was further added to the resin composition.
A resin composition 2 was produced in the same manner as in Example 1 except for the above matters.

[Example 3: Preparation of resin composition 3]
In Example 1, the bisphenol AF type epoxy resin (“YX7760” manufactured by Mitsubishi Chemical Co., epoxy equivalent: 238) was changed to a biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., epoxy equivalent: 271). In addition, 70 parts of an active ester type curing agent (“HPC-8000-65T” manufactured by DIC, a toluene solution having an active group equivalent of about 223 and a solid content of 65 mass%) was used as an active ester type curing agent (“EXB9416- manufactured by DIC”). 70 BK ", methyl isobutyl ketone solution having a nonvolatile content of 70% by mass and an active group equivalent of about 330). Further, the amount of phenolic curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151, solid content of 50% 2-methoxypropanol solution) was changed from 6 parts to 12 parts.
A resin composition 3 was produced in the same manner as in Example 1 except for the above matters.

[Comparative Example 1: Preparation of resin composition 4]
A resin composition 4 was prepared in the same manner as in Example 1 except that 3 parts of the phosphazene resin (“SPS-100” manufactured by Otsuka Chemical Co., Ltd.) was not used.

[Comparative Example 2: Preparation of resin composition 5]
In Example 1, the spherical silica surface-treated with the treatment filler 1 (N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) (“UFP-30” manufactured by Denka). , Specific surface area 30.7 m ² / g, average particle size 0.078 μm)) is surface-treated with treated filler 2 (N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)). Resin composition 5 was prepared in the same manner as in Example 1 except that spherical silica (“UFP-30” manufactured by Denka Co., specific surface area 30.7 m ² / g, average particle diameter 0.3 μm) was used. ..

[Comparative Example 3: Preparation of resin composition 6]
In Example 1, spherical filler surface-treated with treatment filler 1 (N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2) (“UFP-30” manufactured by Denka). , Specific surface area 30.7 m ² / g, average particle size 0.3 μm) with treated filler 3 (N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2). The surface was changed to spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., specific surface area 5.9 m ² / g, average particle size 0.5 μm). Further, the cartridge filter used for filtration was changed from the cartridge filter (“SHP100” manufactured by ROKITECHNO) to the cartridge filter (“SHP020” manufactured by ROKITECHNO).
A resin composition 6 was produced in the same manner as in Example 1 except for the above matters.

[Evaluation methods]
The resin compositions obtained in the above Examples and Comparative Examples were evaluated by the methods described below.

[Production of resin sheet]
As a support, a PET film (“Lumirror R80” manufactured by Toray, thickness 38 μm, softening point 130 ° C.) release-treated with an alkyd resin-based release agent (“AL-5” manufactured by Lintec Co., Ltd.) was prepared.

(Production of resin sheet A)
Each resin composition was uniformly applied on a support by a die coater so that the thickness of the resin composition layer after drying was 6 μm. The applied resin composition was dried at 80 ° C. for 1 minute to obtain a resin composition layer on the support. Then, on the surface of the resin composition layer that was not bonded to the support, the rough surface of the polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex, thickness 15 μm) as a protective film was used as the resin composition layer. Laminated to be joined. Thus, a “resin sheet A” including the support, the resin composition layer, and the protective film in this order was obtained.

(Production of resin sheet B)
Each resin composition was uniformly applied on a support by a die coater so that the thickness of the resin composition layer after drying was 10 μm. The applied resin composition was dried at 80 ° C. for 2 minutes to obtain a resin composition layer on the support. Then, on the surface of the resin composition layer that was not bonded to the support, the rough surface of the polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex, thickness 15 μm) as a protective film was used as the resin composition layer. Laminated to be joined. Thus, a “resin sheet B” including the support, the resin composition layer, and the protective film in this order was obtained.

[I. Measurement of insulation layer thickness and insulation reliability between conductor layers]
(Preparation of evaluation substrate)
(1) Substrate treatment of inner layer circuit board:
As an inner layer circuit board, a glass cloth substrate epoxy resin double-sided copper clad laminate having a circuit conductor (copper) formed on a wiring pattern of L / S (line / space) = 2 μm / 2 μm on both sides (thickness of copper foil) "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Inc., size: 3 μm, substrate thickness: 0.15 mm, size: 255 × 340 mm) was prepared. Both surfaces of the inner layer circuit board were treated with "FlatBOND-FT" manufactured by MEC Co., Ltd. to perform an organic film treatment on the copper surface.

(2) Lamination of resin sheet:
Peel off the protective film from the resin sheet A, and use a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., 2 stage build-up laminator "CVP700") so that the resin composition layer is in contact with the inner layer circuit board. Laminated on both sides of the circuit board. Lamination was performed by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing pressure bonding for 45 seconds at 130 ° C. and a pressure of 0.74 MPa. Then, hot pressing was performed for 75 seconds at 120 ° C. and a pressure of 0.5 MPa.

(3) Thermosetting of the resin composition layer:
The laminated resin sheet and inner layer circuit board are placed in an oven at 130 ° C. and heated for 30 minutes, then transferred to an oven at 170 ° C. and then heated for 30 minutes to thermally cure the resin composition layer to obtain a thickness. Formed an insulating layer having a thickness of 5 μm. Then, the support was peeled off. As a result, a “substrate A” including the insulating layer, the inner layer circuit board and the insulating layer in this order was obtained.

(4) Formation of via holes:
A laser processing machine was used to form a via hole in the insulating layer of the substrate A so as to open on the circuit conductor of the inner layer circuit substrate.

(5) Step of performing roughening treatment:
Desmear treatment as roughening treatment was performed on the insulating layer of the substrate A. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
It was immersed in a swelling solution (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes. Then, it was immersed in an oxidizing agent solution (“Concentrate Compact CP” manufactured by Atotech Japan Co., an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes. Then, it was immersed for 5 minutes at 40 ° C. in a neutralizing solution (“Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd., sulfuric acid aqueous solution). Then, it dried at 80 degreeC for 15 minutes. The substrate A that has been subjected to this wet desmear treatment is referred to as “roughened substrate A”.

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

1. Alkaline cleaning (cleaning the surface of the insulating layer with via holes and adjusting the charge):
The surface of the roughened substrate A was washed at 60 ° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning of via holes):
The surface of the roughened substrate A was treated with an aqueous solution of sodium peroxodisulfate acidified with sulfuric acid at 30 ° C. for 1 minute.
3. Predip (adjustment of electric charge on the surface of the insulating layer to impart Pd):
When the surface of the roughened substrate A is Pre. Dip Neoganth B (trade name) was used for treatment at room temperature for 1 minute.
4. Activator application (application of Pd to the surface of the insulating layer):
The surface of the roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35 ° C. for 5 minutes.
5. Reduction (reduces Pd applied to the insulating layer):
The surface of the roughened substrate A was replaced with a Reducer Neoganth WA (trade name) and a Reducer Accelerator 810 mod. Using a mixed solution with (trade name), the mixture was treated at 30 ° C. for 5 minutes.
6. Electroless copper plating step (Cu is deposited on the surface of the insulating layer (Pd surface)):
The surface of the roughened substrate A is a Basic Solution Printganth MSK-DK (trade name), a Copper solution Printganth MSK (trade name), a Stabilizer Printganth MSK-DK (trade name), and a mixed name of Reducer Cu. The solution was treated at 35 ° C. for 20 minutes. As a result, an electroless copper plating layer (thickness 0.8 μm) was formed on the surface of the insulating layer.

(6-2) Electrolytic plating step:
Then, an electrolytic copper plating step was performed using a chemical solution manufactured by Atotech Japan under the condition that copper was filled in the via holes. Thereafter, as a resist pattern for patterning by etching, a pattern (land pattern) for forming a land having a diameter of 1 mm that is conducted to a lower layer conductor (that is, a circuit conductor of the inner layer circuit board) through a via hole, and the lower layer A conductor layer (thickness 10 μm) having a land and a circular conductor was formed on the surface of the insulating layer using a pattern (circular conductor pattern) for forming a circular conductor having a diameter of 10 mm which was not connected to the conductor. Next, annealing treatment was performed at 200 ° C. for 90 minutes. The substrate thus obtained is referred to as “evaluation substrate B”.

[Measurement of thickness of insulating layer between conductor layers]
The cross-section of the evaluation substrate B was observed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Inc.). Specifically, a cross section perpendicular to the surface of the conductor layer was carved by FIB (Focused Ion Beam), and the cross section was photographed. The thickness of the insulating layer between the conductor layers was measured from the obtained cross-sectional SEM image. For each sample, five randomly selected cross-sectional SEM images were observed, and the average value was used as the thickness (μm) of the insulating layer between the conductor layers, and the results are shown in the table below.

[Evaluation of insulation reliability of insulation layer]
A highly-accelerated life test apparatus (using a 10 mm diameter circular conductor side of the evaluation substrate B obtained above as a + electrode and a grid conductor (copper) side of an inner layer circuit substrate connected to a land having a diameter of 1 mm as a-electrode ( Using "PM422" manufactured by ETAC Co., Ltd.), it was allowed to stand for 200 hours under the conditions of 130 ° C., 85% relative humidity and 3.3V DC voltage application. Then, the insulation resistance value was measured with an electrochemical migration tester (“ECM-100” manufactured by J-RAS).

The above-mentioned measurement was performed for each of the six evaluation substrates B in each of Examples and Comparative Examples. In all of the six evaluation substrates B, the case where the resistance value was 1 × 10 ⁷ Ω or more was “◯”, and the case where even one was less than 1 × 10 ⁷ Ω was “x”. The evaluation results are shown in the following table together with the insulation resistance value. The insulation resistance value shown in the following table is the minimum insulation resistance value of the six test substrates B.

[II. Evaluation of haloing]
(1) Substrate treatment of inner layer circuit board:
As the inner layer circuit board, a glass cloth base epoxy resin double-sided copper clad laminate having inner layer circuits (copper) on both sides (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) was prepared. Both surfaces of the inner layer circuit board were etched by 1 μm with “CZ8101” manufactured by MEC Co., Ltd. to roughen the copper surface.

(2) Lamination of resin sheet:
Peel off the protective film from the resin sheet B, and use a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., 2 stage build-up laminator "CVP700") so that the resin composition layer is in contact with the inner layer circuit board. Laminated on both sides of the circuit board. Lamination was performed by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing pressure bonding for 45 seconds at 130 ° C. and a pressure of 0.74 MPa. Then, hot pressing was performed for 75 seconds at 120 ° C. and a pressure of 0.5 MPa.

(3) Curing of resin composition:
The laminated resin sheet and inner layer circuit board were heated at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes to cure the resin composition layer and form an insulating layer having a thickness of 10 μm. In the haloing evaluation test, this thickness of 10 μm corresponds to the thickness of the insulating layer between the conductor layers in the evaluation substrate D described later.

(4) Via hole formation:
A CO ₂ laser processing machine (“605GTWIII (-P)” manufactured by Mitsubishi Electric Corporation) is used to irradiate the insulating layer with laser light, and the insulating layer has a plurality of via holes each having a top diameter (diameter) of about 30 μm. Formed. The irradiation conditions of the laser light 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). After that, the support was peeled off to obtain a “pre-roughening substrate C” including an insulating layer, an inner layer circuit board and an insulating layer in this order.

(5) Roughening treatment:
The pre-roughening substrate C was immersed in a swelling solution (Swelling dip Securigant P (glycol ethers, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd.) at 60 ° C. for 10 minutes. Next, the substrate C was immersed in a roughening solution (concentrate compact P (KMnO ₄ : 60 g / L, aqueous solution of NaOH: 40 g / L) manufactured by Atotech Japan) at 80 ° C. for 20 minutes. After that, the substrate C was immersed in a neutralizing solution (Reduction Shoryushin Securigant P (aqueous solution of sulfuric acid) manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes. Then, the substrate C was dried at 80 ° C. for 30 minutes to obtain an “evaluation substrate D”.

(6) Plating by semi-additive method:
The evaluation substrate D was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C. for 5 minutes. Next, it was immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Then, it heats at 150 degreeC for 30 minute (s), and performed the annealing process. After that, an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Next, annealing treatment was performed at 200 ° C. for 60 minutes to obtain an “evaluation substrate E”.

[Measurement of via hole size and haloing distance after roughening treatment]
The evaluation substrate D was subjected to cross-section observation using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Inc.). Specifically, FIB (Focused Ion Beam) was used to cut out the insulating layer so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole appears. This cross section was observed by SEM. From the observed image, the bottom diameter and the top diameter of the via hole were measured. Further, in the image observed by the SEM, a gap portion was formed continuously from the edge of the via bottom and formed by peeling the insulating layer from the copper foil layer of the inner layer substrate. Therefore, from the observed image, the distance from the center of the via bottom to the edge of the via bottom (corresponding to the inner radius of the gap) r3 and the distance from the center of the via bottom to the end on the far side of the gap (the gap R4 (corresponding to the outer peripheral radius of r) and the difference r4-r3 between these distances r3 and r4 was calculated as the haloing distance from the edge of the via bottom at the measurement point.

  The above measurement was carried out at 5 randomly selected via holes. Then, the average of the measured top diameters of the five via holes was adopted as the top diameter Lt of the sample after the roughening treatment. The average of the measured bottom diameters of the five via holes was adopted as the bottom diameter Lb of the sample after the roughening treatment. Further, the average of the measured haloing distances of the five via holes was adopted as the haloing distance Wb from the edge of the via bottom of the sample.

  From the above measurement results, the taper rate (the ratio "Lb / Lt" between the top diameter Lt and the bottom diameter Lb of the via hole), the haloing ratio Hb (the haloing distance Wb from the edge of the via bottom after the roughening treatment), The ratio "Wb / (Lb / 2)" of the via hole after the roughening treatment to the radius (Lb / 2) of the via bottom was calculated. When the haloing ratio Hb was 35% or less, it was judged as "◯", and when the haloing ratio Ht was larger than 35%, it was judged as "x".

[Measurement of peeling strength (peel strength) of plated conductor layer]
The conductor layer of the evaluation substrate E was cut into a rectangular portion having a width of 10 mm and a length of 100 mm. Peel off one end of the rectangular part, grab it with a grabber (Autocom type tester “AC-50C-SL” manufactured by TS E), and pull in the vertical direction at room temperature at a speed of 50 mm / min. I peeled it off. The load (kgf / cm) when peeling off 35 mm was measured as the peel strength.

[result]
The results of Examples and Comparative Examples are shown in the table below. In the table below, the numerical value in the column of the component used for the preparation of the resin composition represents the blending amount of each component (calculated as nonvolatile content).

1 First Conductor Layer 2 Second Conductor Layer 3 Insulating Layer 100 Insulating Layer 100U Surface of Insulating Layer Opposite to Conductor Layer 110 Via Hole 120 Via Bottom 120C Center of Via Bottom 130 Via Top 140 Discolored Area 150 Via Edge of Via Bottom of Via Hole 160 Gap Part 170 Edge of Outer Gap of 180 Gap Edge of Via Top of Via Hole 190 Edge of Outer Part of Discoloration Part 200 Inner Layer Substrate 210 Conductor Layer (First Conductor Layer)
220 second conductor layer 300 printed wiring board

Claims (11)

(A) epoxy resin, (B) curing agent, (C) inorganic filler having a specific surface area of 15 m ² / g or more, (D) compound represented by the following formula (1), and (E) phosphazene compound: A resin composition comprising.
(X-R ^a ) _s Si (OR ^b ) _t (1)
(In formula (1),
X's each independently represent an amino group which may have a substituent,
R ^a's each independently represent a divalent aliphatic hydrocarbon group having 4 or more carbon atoms which may have a substituent,
R ^b's each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms,
s and t represent integers that satisfy 1 ≦ s ≦ 3, 1 ≦ t ≦ 3, and s + t = 4. ) The resin composition according to claim 1, wherein in the formula (1), R ^a represents an alkylene group having 4 or more carbon atoms.   The resin composition according to claim 1, wherein in the formula (1), X represents an arylamino group. The resin composition according to any one of claims 1 to 3, wherein the component (E) is represented by the following formula (2).

(In the formula (2), R ¹ and R ² each independently represent an aryl group which may have a substituent, and n represents an integer of 1 to 23.)   The resin composition according to any one of claims 1 to 4, wherein the amount of the component (C) is 30% by mass or more and 90% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.   The resin composition according to any one of claims 1 to 5, wherein the amount of the component (E) is 0.1% by mass or more and 10% by mass or less with respect to 100% by mass of the nonvolatile component in the resin composition. object.   The resin composition according to claim 1, which is used for forming an insulating layer of a printed wiring board. A support,
A resin sheet comprising a resin composition layer provided on a support and containing the resin composition according to claim 1.   The resin sheet according to claim 8, wherein the resin composition layer has a thickness of 15 μm or less.   A printed wiring board, comprising an insulating layer formed of the cured product of the resin composition according to claim 1.   A semiconductor device comprising the printed wiring board according to claim 10.

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