JP7020378B2 - Resin composition - Google Patents

Description

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

In recent years, there has been a demand for miniaturization of electronic devices, high speed of signals, and high density of wiring. Further, recently, there is an increasing demand for reduction of electric signal loss, and in accordance with this demand, a low dielectric constant and a low thermal expansion rate are required. In order to satisfy these requirements, Patent Document 1 studies an insulating layer using a resin composition containing hollow silica and molten silica.
Further, Patent Document 2 discloses hollow aluminosilicate particles.

Japanese Unexamined Patent Publication No. 2013-173841 Japanese Unexamined Patent Publication No. 2016-120126

A conductor layer may be formed on the insulating layer of the printed wiring board. However, in the printed wiring board provided with the conductor layer formed on the insulating layer in this way, blister may occur at the time of reflow. Here, the blister is a phenomenon in which the conductor layer rises and swells during reflow.

Further, the resin composition containing hollow particles such as hollow silica has low process resistance, and the hollow particles may be cracked in the process until the insulating layer is obtained. Here, the process resistance refers to a property that can suppress cracking of hollow particles in the process from the process of producing the resin composition to the process of curing the resin composition to obtain an insulating layer.

The present invention has been devised in view of the above problems, and is a resin composition capable of obtaining an insulating layer capable of suppressing blister during reflow and having excellent process resistance; a resin composition containing the above resin composition. It is an object of the present invention to provide a resin sheet provided with a material layer; and a printed wiring board and a semiconductor device containing a cured product of the resin composition.

The present inventor has diligently studied to solve the above-mentioned problems. As a result, the present inventor has determined that (C) hollow inorganic particles satisfy predetermined requirements in a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) hollow inorganic particles in combination. , And found that the above-mentioned problems can be solved, and completed the present invention.
That is, the present invention includes the following.

[1] Containing (A) epoxy resin, (B) curing agent, and (C) hollow inorganic particles.
(C) A resin composition in which hollow inorganic particles satisfy at least one of the following requirements (c1) and (c2).
(C1): (C) Hollow inorganic particles are formed of an inorganic composite oxide.
(C2): The porosity of the hollow inorganic particles (C) is 25% by volume or more, and the average particle size of the hollow inorganic particles (C) is 5.0 μm or less.
[2] The resin composition according to [1], wherein the amount of the hollow inorganic particles (C) is 50% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition.
[3] The resin composition according to [1] or [2], wherein the hollow inorganic particles are formed of aluminosilicate.
[4] The resin composition according to any one of [1] to [3], wherein the average particle size of the hollow inorganic particles (C) is 2.5 μm or less in the requirement (c2).
[5] The resin composition according to any one of [1] to [4], which contains 3% by mass or more of a liquid component at 20 ° C. with respect to 100% by mass of a non-volatile component in the resin composition.
[6] The resin composition according to any one of [1] to [5], which is used for forming an insulating layer for forming a conductor layer.
[7] Support and
A resin sheet provided on a support and comprising a resin composition layer containing the resin composition according to any one of [1] to [6].
[8] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [6].
[9] A semiconductor device including the printed wiring board according to [8].

According to the present invention, a resin composition capable of obtaining an insulating layer capable of suppressing blisters during reflow and having excellent process resistance; a resin sheet provided with a resin composition layer containing the above resin composition; A printed wiring board and a semiconductor device containing a cured product of the above resin composition can be provided.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

[1. Outline of resin composition]
The resin composition according to one embodiment of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) hollow inorganic particles. (C) Hollow inorganic particles represent hollow particles formed of an inorganic material. Further, the hollow particles represent particles having pores inside.
Further, the hollow inorganic particles (C) of this resin composition satisfy at least one of the following requirements (c1) and (c2).
(C1): (C) Hollow inorganic particles are formed of an inorganic composite oxide.
(C2): The porosity of the hollow inorganic particles (C) is 25% by volume or more, and the average particle size of the hollow inorganic particles (C) is 5.0 μm or less.

By using this resin composition, it is possible to obtain an insulating layer capable of suppressing blisters during reflow. Hereinafter, the property of the insulating layer capable of suppressing blister during reflow in this way may be referred to as “blister resistance”. Further, this resin composition has excellent process resistance.

[2. (A) Ingredient: Epoxy resin]
Examples of the epoxy resin as the component (A) include a bixilenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, and a 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, glycidylamine type epoxy resin, glycidyl ester Type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy Examples thereof include a resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. (A) One type of epoxy resin may be used alone, or two or more types may be used in combination.

The resin composition preferably contains, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the epoxy resin (A). % 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”) or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ). The resin composition may contain only the liquid epoxy resin or only the solid epoxy resin as the (A) epoxy resin, but may contain a combination of the liquid epoxy resin and the solid epoxy resin. Is preferable. By using the liquid epoxy resin and the solid epoxy resin in combination as the epoxy resin (A), the flexibility of the resin composition can be improved and the breaking strength of the cured product of the resin composition can be improved.

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, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. Alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, and cyclohexane type epoxy are preferable. The resin is more preferable, and the bisphenol A type epoxy resin and the cyclohexane type epoxy resin are 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 Co., Ltd. 828EL "(bisphenol A type epoxy resin);" jER807 "," 1750 "(bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .;" jER152 "(phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "630", "630LSD" (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX" manufactured by Nagase ChemteX. -721 "(glycidyl ester type epoxy resin);" seroxide 2021P "manufactured by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton);" PB-3600 "manufactured by Daicel Co., Ltd. (epoxy resin having a butadiene structure); Examples thereof include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Sumikin Chemical Co., Ltd. These may be used individually by 1 type, or may be used in combination of 2 or more types.

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

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, bixirenol type epoxy resin, naphthalene type epoxy resin, biphenyl type. Epoxy resins, naphthylene ether type epoxy resins and bisphenol A type epoxy resins are more preferred.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalen type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200" (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" manufactured by DIC Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku Co., Ltd .; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin); "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000H", "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YX8800" (anthracen type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" and "YX7760" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol AF type epoxy resin); Mitsubishi Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. and the like can be mentioned. .. These may be used individually by 1 type, or may be used in combination of 2 or more types.

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is a mass ratio, preferably 1: 1 to 1:20. , More preferably 1: 1.5 to 1:15, and particularly preferably 1: 2 to 1:13. When the quantitative ratio of the liquid epoxy resin to the solid epoxy resin is in such a range, the process resistance and the blister resistance can be effectively enhanced. In addition, when used in the form of a resin sheet, appropriate adhesiveness and sufficient flexibility are usually obtained, and handleability is improved. Further, usually, a cured product having sufficient breaking strength can be obtained.

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

The weight average molecular weight (Mw) of the epoxy resin (A) is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of effectively enhancing process resistance and blister resistance.

The weight average molecular weight of the resin can be measured as a polystyrene-equivalent 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 Corporation as a column, and chloroform as a mobile phase. The column temperature can be measured at 40 ° C. and calculated using a calibration curve of standard polystyrene.

The amount of the (A) epoxy resin in the resin composition is preferably 1% by mass with respect to 100% by mass of the non-volatile component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. As mentioned above, it is more preferably 5% by mass or more, still more preferably 10% 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 or less, from the viewpoint of effectively enhancing the process resistance and the blister resistance.

[3. (B) Ingredient: Hardener]
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 an active ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, a carbodiimide-based curing agent, and an amine-based curing agent. , Acid anhydride type curing agent and the like. Further, (B) the curing agent may be used alone or in combination of two or more.

As the active ester-based 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 such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. The compound to have is preferable. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..

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

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

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. Examples thereof include active ester-based curing agents containing a benzoylated product of phenol novolac. Of these, 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 consisting of phenylene-dicyclopentylene-phenylene.

Commercially available products of the active ester-based curing agent include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and "HPC-8000H" as active ester-based 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 curing agent; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent containing an acetylated product of phenol novolac; benzoyl of phenol novolac. "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent containing a compound; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac; Examples of the ester-based curing agent include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); and the like.

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

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", 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 & Sumitomo Metal Corporation. 395 ";" TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "," EXB-9500 "; etc. manufactured by DIC Corporation.

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 .; "Pd" manufactured by Shikoku Chemicals Corporation. "FA" can be mentioned.

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylencyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidendiphenyl disyanate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Examples thereof include polyfunctional cyanate resins derived from phenol novolak, cresol novolak, and the like; prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BADBy" manufactured by Ronza Japan. (Bisphenol A dicyanate), "BA230", "BA230S75" (prepolymer in which a part or all of bisphenol A dicyanate is triazined to form a trimer) and the like can be mentioned.

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

Examples of the amine-based curing agent include curing agents having one or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. 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-xylylene diamine, diethyltoludiamine, 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, Examples thereof include bis (4- (3-aminophenoxy) phenyl) sulfone. Commercially available products may be used as the amine-based curing agent, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard AB", "Kayahard AB" manufactured by Nippon Kayaku Corporation. Examples include "Kayahard AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

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, methyltetrahydrohydride phthalic acid, methylhexahydrohydride phthalic acid, methylnadic acid anhydride, and hydride methylnadic acid. Anhydride, Trialkyltetrahydrophthalic anhydride, Dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-franyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, Trianhydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized, and the like. Examples of commercially available acid anhydride-based curing agents include "HNA-100" and "MH-700" manufactured by Shin Nihon Rika Co., Ltd.

Among the above, the curing agent (B) includes an active ester-based curing agent, a phenol-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent from the viewpoint of effectively enhancing process resistance and blister resistance. A curing agent is preferable, an active ester-based curing agent, a phenol-based curing agent and a carbodiimide-based curing agent are more preferable, and an active ester-based curing agent is particularly preferable. When the active ester-based curing agent is used, (B) the content of the active ester-based curing agent with respect to 100% by mass of the curing agent is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more. It is usually 100% by mass or less, preferably 98% by mass or less, more preferably 96% by mass or less, and further preferably 94% by mass or less.

The amount of the (B) curing agent in the resin composition is preferably 1% by mass or more, more preferably 1% by mass or more, based on 100% by mass of the non-volatile component in the resin composition from the viewpoint of effectively enhancing the process resistance and the blister resistance. It is 5% by mass or more, more preferably 10% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.

When the number of epoxy groups of the (A) epoxy resin is 1, the number of active groups of the (B) curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and is preferable. Is 3 or less, more preferably 2.0 or less, still more preferably 1.6 or less. Here, the "(A) number of epoxy groups in the epoxy resin" is a total value obtained by dividing the mass of the non-volatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. The "(B) number of active groups of the curing agent" is a total value obtained by dividing the mass of the non-volatile component of the (B) curing agent present in the resin composition by the active group equivalent. When the number of active groups of the (B) curing agent is in the above range when the number of epoxy groups of the (A) epoxy resin is 1, the process resistance and blister resistance can be effectively enhanced, and more usually, the resin composition. The heat resistance of the cured product is further improved.

[4. (C) component: hollow inorganic particles]
The resin composition contains hollow inorganic particles as the component (C) that satisfy at least one of the requirements (c1) and (c2). By using the hollow inorganic particles (C), excellent process resistance and blister resistance can be achieved. Further, usually, the dielectric constant and the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced.
Hereinafter, each of the requirement (c1) and the requirement (c2) will be described in detail.

First, the requirement (c1) will be described. The hollow inorganic particles (C) satisfying the requirement (c1) are formed of an inorganic composite oxide. The inorganic composite oxide represents an oxide containing two or more kinds of atoms selected from the group consisting of metal atoms and metalloid atoms. As such an inorganic composite oxide, an oxide containing a combination of silicon and one or more kinds of atoms selected from the group consisting of metal atoms other than silicon and metalloid atoms is preferable. Examples of the metal atom to be combined with silicon include aluminum, lead, nickel, cobalt, copper, zinc, zirconium, iron, lithium, magnesium, barium, potassium, calcium, titanium, boron, sodium and the like, and aluminum is particularly preferable. .. Therefore, as the inorganic composite oxide, an oxide containing silicon and aluminum is preferable, and aluminosilicate is particularly preferable.

In the structural composition of the aluminosilicate, the content of SiO ₂ is preferably 70% by mass to 90% by mass, more preferably 75% by mass to 85% by mass, and particularly preferably about 80% by mass. The content of Al ₂ O ₃ is preferably 10% by mass to 30% by mass, more preferably 15% by mass to 25% by mass, and particularly preferably about 20% by mass. When an aluminosilicate having such a composition is used, process resistance and blister resistance can be effectively enhanced.

The aluminosilicate may contain Fe ₂ O ₃ in its structural composition. However, the content of Fe ₂ O ₃ is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.6% by mass or less, and it is particularly preferable that Fe ₂ O ₃ is not contained. preferable. When an aluminosilicate having such a small amount of Fe ₂ O ₃ is used, process resistance and blister resistance can be effectively enhanced.

Further, the aluminosilicate may contain an alkali metal oxide and an alkaline earth metal oxide in its structural composition. However, the content of the alkali metal oxide and the alkaline earth metal oxide is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably does not contain the alkali metal oxide and the alkaline earth metal oxide. preferable. When aluminosilicates containing such a small amount of alkali metal oxides and alkaline earth metal oxides are used, process resistance and blister resistance can be effectively enhanced.

The porosity of the hollow inorganic particles (C) satisfying the requirement (c1) is arbitrary, and may be, for example, 5% by volume or more, 10% by volume or more, 15% by volume or more, 20% by volume or more, and the like. Above all, from the viewpoint of effectively enhancing the process resistance and the blister resistance, the porosity of the hollow inorganic particles (C) satisfying the requirement (c1) is preferably within the range described in the requirement (c2).

The porosity represents the volume ratio of the hollow portion in (C) hollow inorganic particles. This porosity can be calculated from the density of hollow inorganic particles. The specific measurement method may be as follows. The density of the hollow inorganic particles is measured using a true density measuring device. This measurement uses nitrogen as the measuring gas. As the true density measuring device, for example, ULTRAPY CNOMETER 1000 manufactured by QUANTACHROME can be used. Then, using the measured density and the material density of the inorganic material forming the hollow inorganic particles, the porosity can be calculated according to the following formula (X).
Pore ratio (% by volume) = {1- (measured density [g / cm ³ ] / material density of inorganic material [g / cm ³ ])} x 100 (X)

The average particle size of the hollow inorganic particles (C) satisfying the requirement (c1) is arbitrary, and may be, for example, 10 μm or less, 5 μm or less, and the like. Above all, from the viewpoint of effectively enhancing the process resistance and the blister resistance, the average particle size of the hollow inorganic particles (C) satisfying the requirement (c1) is preferably within the range described in the requirement (c2).

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

The method for producing (C) hollow inorganic particles satisfying the above-mentioned requirement (c1) is arbitrary. For example, the hollow inorganic particles (C) satisfying the requirement (c1) can be produced by the method described in JP-A-2016-120126.

Next, the requirement (c2) will be described. The hollow inorganic particles (C) satisfying the requirement (c2) have a porosity of 25% by volume or more and an average particle size of 5.0 μm or less.

Specifically, the porosity of the hollow inorganic particles (C) satisfying the requirement (c2) is usually 25% by volume or more, preferably 30% by volume or more, more preferably 40% by volume or more, still more preferably 50% by volume or more. It is preferably 90% by volume or less, more preferably 85% by volume or less, and particularly preferably 80% by volume or less. (C) When the hollow inorganic particles have a porosity in such a range, process resistance and blister resistance can be effectively enhanced. Further, usually, the dielectric constant and the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced.

The average particle size of the hollow inorganic particles (C) satisfying the requirement (c2) is usually 5.0 μm or less, preferably 3.0 μm or less, more preferably 2.5 μm or less, still more preferably 2.0 μm or less, particularly. It is preferably 1.6 μm or less. (C) When the hollow inorganic particles have an average particle size in such a range, process resistance and blister resistance can be effectively enhanced. Further, usually, the dielectric constant and the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced. The lower limit of the average particle size is arbitrary, and may be, for example, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, and the like.

Any inorganic material can be used as the material of the hollow inorganic particles (C) satisfying the requirement (c2). Examples of this inorganic material include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, and hydroxide. Magnesium, 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, titanium Examples thereof include barium acid, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and aluminosilicate. Further, examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Among them, the inorganic composite oxide described in the requirement (c1) is preferable as the material of the hollow inorganic particles (C) satisfying the requirement (c2).

The method for producing (C) hollow inorganic particles satisfying the above-mentioned requirement (c2) is arbitrary. For example, the hollow inorganic particles (C) satisfying the requirement (c2) can be produced by the methods described in JP-A-2016-120126 and JP-A-2015-155373.

(C) The hollow inorganic particles may satisfy only one of the above-mentioned requirements (c1) and (c2), but it is preferable that both of them are satisfied. By using (C) hollow inorganic particles that satisfy both the requirement (c1) and the requirement (c2), process resistance and blister resistance can be enhanced particularly effectively.

(C) As the hollow inorganic particles, one type may be used alone, or two or more types may be used in combination.

(C) The hollow inorganic particle generally has a hollow portion formed in the particle and an outer shell portion formed of an inorganic material surrounding the hollow portion. Normally, the hollow portion is partitioned from the outside of the particle by the outer shell portion. At this time, it is desirable that the hollow portion does not communicate with the outside of the particles. Therefore, it is desirable that the outer shell portion is an airless shell having no pores communicating the hollow portion and the outside of the particles. By using such (C) hollow inorganic particles, process resistance and blister resistance can be effectively enhanced. It can be confirmed by observing with a transmission electron microscope (TEM) that the outer shell portion has no pores. Such hollow inorganic particles (C) can be produced by the method described in JP-A-2016-120126, and can be obtained as hollow aluminosilicate particles "MG-005" manufactured by Taiheiyo Cement.

(C) The specific surface area of the hollow inorganic particles is preferably 60 m ² / g or less, more preferably 40 m ² / g or less, and particularly preferably 15 m ² / g or less. (C) When the hollow inorganic particles have a specific surface area in the above range, process resistance and blister resistance can be effectively enhanced. Further, usually, the dielectric constant and the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced. (C) The lower limit of the specific surface area of the hollow inorganic particles is not particularly limited and may be, for example, 1 m ² / g. The specific surface area is calculated by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (“Macsorb HM-1210” manufactured by Mountech) according to the BET method and using the BET multipoint method.

(C) The hollow inorganic particles are preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, and titanate-based agents. Coupling agents and the like can be mentioned. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) and the like.

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of (C) improving the dispersibility of the hollow inorganic particles. Specifically, 100 parts by mass of the hollow inorganic particles (C) are preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, and 0.2 parts by mass to 3 parts by mass are surface-treated. It is preferably treated, and it is preferable that the surface is treated with 0.3 parts by mass to 2 parts by mass.

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

The amount of carbon per unit surface area of the hollow inorganic particles can be measured after the hollow inorganic particles after the surface treatment are washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the hollow inorganic particles surface-treated with a surface treatment agent, and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the hollow inorganic particles can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The amount of the hollow inorganic particles (C) in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, based on 100% by mass of the non-volatile component in the resin composition. It is particularly preferably 25% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. (C) When the amount of hollow inorganic particles is in the above range, process resistance and blister resistance can be effectively enhanced. Further, usually, the dielectric constant and the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced, or the mechanical strength of the cured product can be increased.

It is represented by the following formula (c3) using the mass Mt of the non-volatile component in the resin composition, the mass Mc of the hollow inorganic particles (C), and the porosity Rp [%] of the hollow inorganic particles (C). A reduction ratio R (c3) [%] is defined. In this reduction ratio R (c3), "{Rp / (100-Rp)} x Mc" is the volume of the hollow portion of a certain (C) hollow inorganic particle and the inorganic material forming the (C) hollow inorganic particle. It corresponds to the product with the material density, and thus represents the mass of the inorganic material by the volume of the hollow portion of the (C) hollow inorganic particles. Further, "Σ (Rp / (100-Rp) × Mc)" represents the total mass of the inorganic material by the volume of the hollow portion of all (C) hollow inorganic particles contained in the resin composition. Therefore, the denominator of the second term in the brackets on the right side of the formula (c3) is the mass of the non-volatile component of the resin composition assuming that the hollow portion is filled with the inorganic material of the hollow inorganic particles (C). show. Therefore, the reduction ratio R (c3) has the same composition as the resin composition according to the present embodiment except that the resin composition containing the inorganic particles having no hollow portion (that is, the hollow portion is filled with the inorganic material). It shows how much the mass of the resin composition according to the present embodiment containing (C) hollow inorganic particles can be reduced by the hollow portion as compared with the resin composition). From the viewpoint of effectively enhancing process resistance and blister resistance, the reduction ratio R (c3) of the resin composition according to the present embodiment is preferably 7% or more, more preferably 10% or more, and particularly preferably 15% or more. Yes, preferably 70% or less, more preferably 60% or less, and particularly preferably 50% or less.

[5. (D) Component: Thermoplastic resin]
The resin composition may further contain any component in addition to the above-mentioned components. For example, the resin composition may contain (D) a thermoplastic resin as an arbitrary component.

Examples of the thermoplastic resin as the component (D) 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 effectively enhancing the process resistance and the blister resistance, and from the viewpoint of obtaining an insulating layer having a small surface roughness and particularly excellent adhesion to the conductor layer. Further, the thermoplastic resin 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, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpene. Examples thereof include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or 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); "YX8100" manufactured by Mitsubishi Chemical Corporation (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical Corporation. "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, Examples thereof include "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482";

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 "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", and "Electrified Butyral 6000-EP" manufactured by Sekisui Chemical Co., Ltd .; Sekisui Chemical Co., Ltd. Examples thereof include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by the same company.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by NEW JAPAN CHEMICAL CO., LTD. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-31386).

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

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

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

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

(D) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 70,000 or less, more preferably 70,000 or less. It is 60,000 or less, particularly preferably 50,000 or less. (D) When the weight average molecular weight (Mw) of the thermoplastic resin is within the above range, process resistance and blister resistance can be effectively enhanced. Further, usually, the dielectric constant and the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced, or the mechanical strength of the cured product can be increased.

When the (D) thermoplastic resin is used, the amount of the (D) thermoplastic resin in the resin composition is preferably 0.1% by mass or more, more preferably 0.1% by mass, based on 100% by mass of the non-volatile component in the resin composition. Is 0.5% by mass or more, more preferably 1% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less. (D) When the amount of the thermoplastic resin is in the above range, the process resistance and the blister resistance can be effectively enhanced. Further, usually, the dielectric constant and the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced, or the mechanical strength of the cured product can be increased.

[6. (E) Ingredient: Curing accelerator]
In addition to the above-mentioned components, the resin composition may further contain (E) a curing accelerator as an arbitrary component.

Examples of the (E) curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Of these, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

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

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (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, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline Examples thereof include imidazole compounds such as 2-phenylimidazolin and adducts of the imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, 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, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylviguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned, with dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene being preferred.

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

When the (E) curing accelerator is used, the amount of the (E) curing accelerator in the resin composition is preferably 0.01% by mass or more, more preferably 0.01% by mass, based on 100% by mass of the non-volatile component in the resin composition. Is 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1.5% by mass or less. (E) When the amount of the curing accelerator is in the above range, process resistance and blister resistance can be effectively enhanced. Further, usually, the dielectric constant and the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced, or the mechanical strength of the cured product can be increased.

[7. (F) component: maleimide compound]
The resin composition may further contain the (F) maleimide compound as an arbitrary component in addition to the above-mentioned components. The (F) maleimide compound is a compound containing a maleimide group represented by the following formula (F1) in the molecule. (F) By using the maleimide compound, the heat resistance of the cured product of the resin composition can be enhanced.

Examples of the maleimide compound (F) include 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4, 4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4 '-Diphenylsulphonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene and the like can be mentioned.

(F) Specific examples of the maleimide compound include "BMI-1000" manufactured by Daiwa Kasei Kogyo Co., Ltd., "BMI" manufactured by KI Kasei Co., Ltd. (4,4'-diphenylmethanebismaleimide); "BMI-" manufactured by Daiwa Kasei Kogyo Co., Ltd. 2000 ”(polyphenylmethane maleimide); Daiwa Kasei Kogyo Co., Ltd.“ BMI-3000 ”(m-phenylene bismaleimide); Daiwa Kasei Kogyo Co., Ltd.“ BMI 4000 ”, Keiai Kasei Co., Ltd.“ BMI-80 ”(bisphenol A) Diphenyl ether bismaleimide); "BMI5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., "BMI-70" manufactured by KI Kasei Co., Ltd. (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide); Daiwa Kasei Kogyo Co., Ltd. "BMI-7000" (4-methyl-1,3-phenylene bismaleimide); Daiwa Kasei Kogyo Co., Ltd. "BMI-TMH" (1,6'-bismaleimide- (2,2,4-) Trimethyl) hexane); Daiwa Kasei Kogyo Co., Ltd. "BMI-6000" (4,4'-diphenyl ether bismaleimide); Daiwa Kasei Kogyo Co., Ltd. "BMI-8000" (4,4'-diphenylsulphon bismaleimide); 1,3-Bis (3-maleimidephenoxy) benzene manufactured by Kogyo Co., Ltd .; 1,3-bis (4-maleimidephenoxy) benzene manufactured by Daiwa Kasei Kogyo Co., Ltd .; "ANILIX-MI" manufactured by Mitsui Kagaku Fine Co., Ltd .; etc. Be done. (F) The maleimide compound may be used alone or in combination of two or more.

The amount of the (F) maleimide compound in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more with respect to 100% by mass of the non-volatile component in the resin composition. It is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. (F) When the amount of the maleimide compound is within the above range, the heat resistance of the cured product of the resin composition can be enhanced.

[8. (G) Ingredient: Phosphazen compound]
The resin composition may further contain the (G) phosphazene compound as an arbitrary component in addition to the above-mentioned components. The phosphazen compound refers to a compound containing a structural unit represented by -P = N-. Examples of the (G) polyphosphazene compound include a cyclophosphazene compound having a cyclic structure composed of a structural unit represented by −P = N— and a chain structure composed of a structural unit represented by −P = N−. Examples thereof include polyphosphazene compounds having. Among them, a cyclophosphazen compound is preferable, and a cyclophosphazen compound having a phenolic hydroxyl group is particularly preferable. By using the (G) phosphazene compound, the elastic modulus of the cured product of the resin composition can be lowered and the mechanical strength of the insulating layer can be improved. Further, by using the (G) phosphazene compound, the flame retardancy of the insulating layer can usually be improved.

Specific examples of the (G) phosphazen compound include, for example, "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Otsuka Chemical Co., Ltd .; "FP-" manufactured by Fushimi Pharmaceutical Co., Ltd. 100 ”,“ FP-110 ”,“ FP-300 ”,“ FP-390 ”,“ FP-400 ”and the like. As the (G) phosphazene compound, one type may be used alone, or two or more types may be used in combination.

The amount of the (G) phosphazene compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1 with respect to 100% by mass of the non-volatile component in the resin composition. It is 5% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less. When the amount of the (G) phosphazene compound is in the above range, the elastic modulus of the cured product of the resin composition can be effectively lowered.

[9. (H) component: radically polymerizable compound]
The resin composition may further contain (H) a radically polymerizable compound as an arbitrary component in addition to the above-mentioned components. (H) The radically polymerizable compound usually has an ethylenic double bond. Then, for example, the polymerization reaction can be caused by irradiation with active energy rays. By using the (H) radically polymerizable compound, the elastic modulus of the cured product of the resin composition can be lowered and the mechanical strength of the insulating layer can be improved. Further, usually, the dielectric loss tangent of the cured product of the resin composition can be lowered.

(H) The radically polymerizable compound usually contains a radically polymerizable unsaturated group containing an ethylenically double bond in the molecule. Examples of the radically polymerizable unsaturated group include a vinyl group, a vinylphenyl group, an acryloyl group, and a methacryloyl group, a maleimide group, a fumaroyl group, and a maleoil group. (H) The radically polymerizable compound preferably has two or more radically polymerizable unsaturated groups per molecule. Further, the (H) radically polymerizable compound preferably contains a cyclic structure such as an alicyclic structure and an aromatic ring structure in the molecule.

Examples of the radically polymerizable compound (H) include the compounds shown below.

(N1 and m1 represent an integer of 0 to 300. However, except when one of n1 and m1 is 0. As n1 and m1, it is preferable to represent an integer of 1 to 100. It is more preferable to represent an integer, and even more preferably to represent an integer of 1 to 10. n1 and m1 may be the same or different.)

Specific examples of the (H) radically polymerizable compound include "OPE-2St" and "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, "A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., and "A-DOG" manufactured by Kyoeisha Chemical Co., Ltd. Examples thereof include "DCP-A". (H) The radically polymerizable compound may be used alone or in combination of two or more.

The number average molecular weight of the radically polymerizable compound (H) is preferably 3000 or less, more preferably 2500 or less, still more preferably 2000 or less and 1500 or less. The lower limit is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, and 1000 or more. The number average molecular weight is a polystyrene-equivalent number average molecular weight measured using gel permeation chromatography (GPC).

The amount of the (H) radically polymerizable compound in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass with respect to 100% by mass of the non-volatile component in the resin composition. The above is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. (H) When the amount of the radically polymerizable compound is in the above range, the elastic modulus of the cured product of the resin composition can be effectively lowered.

[10. (I) Ingredient: Polymerization Initiator]
In addition to the above-mentioned components, the resin composition may further contain (I) a polymerization initiator as an arbitrary component. The (I) polymerization initiator has a function of accelerating the polymerization of the (H) radically polymerizable compound.

(I) Examples of the polymerization initiator include t-butylcumyl peroxide, t-butylperoxyacetate, α, α'-di (t-butylperoxy) diisopropylbenzene, t-butylperoxylaurate, and t. Examples thereof include peroxides such as -butylperoxy-2-ethylhexanoate t-butylperoxyneodecanoate and t-butylperoxybenzoate.

(I) Specific examples of the polymerization initiator include "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", "Perbutyl ND", and "Perbutyl Z" manufactured by NOF CORPORATION. , "Park Mill P", "Park Mill D" and the like. (I) The polymerization initiator may be used alone or in combination of two or more.

The amount of the (I) polymerization initiator in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.05% by mass, based on 100% by mass of the non-volatile component in the resin composition. It is 0.1% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less.

[11. (J) Component: (C) Inorganic filler other than hollow inorganic particles]
The resin composition may further contain (J) an inorganic filler as an arbitrary component in addition to the above-mentioned components. However, this (J) inorganic filler does not include the above-mentioned (C) hollow inorganic particles.

(J) As the inorganic filler, any particles formed of the inorganic material can be used. As an example of the inorganic material, for example, the inorganic material exemplified as the material of (C) hollow inorganic particles can be arbitrarily used. Further, as the (J) inorganic filler, one type may be used alone, or two or more types may be used in combination.

(J) The average particle size of the inorganic filler is not particularly limited. The specific average particle size is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 1 μm or less. be. The average particle size of (J) the inorganic filler can be measured by the same method as (C) the average particle size of the hollow inorganic particles.

The specific surface area of the (J) inorganic filler may be in the same range as the specific surface area of the (C) hollow inorganic particles. (J) The specific surface area of the inorganic filler can be measured by the same method as (C) the specific surface area of the hollow inorganic particles.

The (J) inorganic filler may be treated with a surface treatment agent in the same manner as the (C) hollow inorganic particles. The example of the surface treatment agent and the degree of surface treatment may be the same as those of (C) hollow inorganic particles.

The amount of the (J) inorganic filler in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more with respect to 100% by mass of the non-volatile component in the resin composition. It is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less.

[12. (K) component: organic filler]
In addition to the above-mentioned components, the resin composition may further contain (K) an organic filler as an arbitrary component. (K) There is no limitation on the type of organic filler. Further, as the (K) organic filler, one type may be used alone, or two or more types may be used in combination.

As the (K) organic filler, rubber particles are preferable from the viewpoint of suppressing warpage of the resin composition. It is preferable that the rubber particles do not dissolve in the organic solvent used when preparing the resin composition, do not dissolve in the resin component in the resin composition, and exist in a dispersed state in the varnish of the resin composition. The resin component of the resin composition refers to a component other than (C) hollow inorganic particles and (J) inorganic filler among the non-volatile components contained in the resin composition. Examples of such rubber particles include core-shell type rubber particles, crosslinked acrylic nitrile butadiene rubber (NBR) particles, crosslinked styrene butadiene rubber (SBR) particles, acrylic rubber particles, and the like. Of these, core-shell type rubber particles are preferable from the viewpoint of suppressing warpage of the cured product and improving developability.

The core-shell type rubber particles are rubber particles including a shell layer on the surface of the particles and a core layer inside the shell layer, and may include an intermediate layer between the shell layer and the core layer. .. Examples of the core-shell type rubber particles include core-shell type rubber particles including a shell layer formed of a glass-like polymer and a core layer formed of a rubber-like polymer; a shell layer formed of a glass-like polymer and a rubber-like material. Core-shell type rubber particles including an intermediate layer formed of a polymer and a core layer formed of a glassy polymer; and the like. Examples of the glassy polymer include a polymer of methyl methacrylate and the like, and examples of the rubbery polymer include a butyl acrylate polymer (butyl rubber) and the like. Specific examples of the core-shell type rubber particles include stafyroids "AC3832" and "AC3816N" manufactured by Aica Kogyo Co., Ltd., "Metabrene KW-4426" manufactured by Mitsubishi Chemical Corporation, and the like.

The average particle size of the (K) organic filler may be in the same range as the average particle size of the (J) inorganic filler. Further, the average particle size of (K) the organic filler can be measured by the same method as (C) the average particle size of the hollow inorganic particles.

The amount of the (K) organic filler in the resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.5% by mass, based on 100% by mass of the non-volatile component in the resin composition. It is 1% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

[13. (L) component: flame retardant]
The resin composition may further contain (L) a flame retardant as an arbitrary component in addition to the above-mentioned components. However, this (L) flame retardant does not include the above-mentioned (G) phosphazene compound. (L) By using a flame retardant, the flame retardancy of the cured product of the resin composition can be enhanced.

Examples of the flame retardant (L) include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. Specific examples of the (L) flame retardant include "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd., and the like. Further, as the flame retardant, one that is hard to be hydrolyzed is preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable. .. (L) The flame retardant may be used alone or in combination of two or more.

The amount of the flame retardant (L) in the resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, still more preferably 1 with respect to 100% by mass of the non-volatile component in the resin composition. It is 0.0% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.

[14. (M) component: other optional components]
The resin composition may further contain any additive in addition to the above-mentioned components. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickeners, defoamers, leveling agents, adhesion-imparting agents, colorants, surfactants and the like. Resin additives; etc. These additives may be used alone or in combination of two or more.

[15. Conditions of composition that can make effective use of the effect]
The amount of the liquid component contained in the resin composition is preferably 3% by mass or more, more preferably 6% by mass or more, and particularly preferably 10% by mass or more, based on 100% by mass of the non-volatile component in the resin composition. .. The above-mentioned "liquid component" refers to a non-volatile component in a resin composition that is liquid at 20 ° C. under normal pressure. According to the study of the present inventor, it has been found that the more the liquid component is contained in the conventional resin composition, the more likely the insulating layer produced from the resin composition is to generate blisters. On the other hand, the above-mentioned resin composition can suppress the generation of blisters even if it has such a composition in which blisters are likely to occur. Therefore, from the viewpoint of effectively utilizing the effect of improving the blister resistance, the resin composition according to the present embodiment preferably has a composition in which blister is likely to occur in the past, and specifically, the above-mentioned amount. It preferably contains a liquid component. The upper limit of the amount of the liquid component is not particularly limited and may be, for example, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less.

[16. Method for manufacturing resin composition]
The above-mentioned resin composition can be produced, for example, by stirring the compounding components using a stirring device such as a rotary mixer and uniformly dispersing them. Stirring may be performed in a state where the resin composition contains an organic solvent. According to the resin composition described above, cracking of the hollow inorganic particles (C) due to such stirring can be suppressed.

[17. Characteristics of resin composition]
The above-mentioned resin composition has excellent process resistance. Therefore, this resin composition can suppress the cracking of (C) hollow inorganic particles in the process of producing the resin composition. Therefore, the resin composition can reduce the proportion of the cracked (C) hollow inorganic particles, and preferably does not contain the cracked (C) hollow inorganic particles.

Further, since the above-mentioned resin composition has excellent process resistance, cracking of (C) hollow inorganic particles can be suppressed in the process of producing an insulating layer using the resin composition. Therefore, the insulating layer formed of the cured product of this resin composition can reduce the proportion of the cracked (C) hollow inorganic particles, and preferably does not contain the cracked (C) hollow inorganic particles.

In one embodiment, the above-mentioned resin composition is stirred in a homomixer (“TK Agi-Homo-Mixer” manufactured by Primix Corporation). This stirring is performed by rotating the homomixer at 7000 rpm for 30 minutes. The resin composition thus stirred is applied onto a substrate, dried to form a resin film, and then heated at 200 ° C. for 90 minutes to be cured to obtain a cured product. In this cured product, the cracked (C) hollow inorganic particles can be eliminated. The presence or absence of the cracked (C) hollow inorganic particles can be confirmed by observing the cross section (observation width 30 μm, observation magnification 9,000 times) using the FIB-SEM composite device. As the specific operation of the process resistance evaluation described above, the method described in [Process resistance evaluation of hollow particles] of Examples can be adopted.

The above-mentioned resin composition has excellent blister resistance. Therefore, by using this resin composition, it is possible to obtain an insulating layer capable of suppressing blisters during reflow.

In one embodiment, a resin composition layer containing the resin composition is formed on the inner layer substrate. Then, the resin composition layer is heated at 180 ° C. for 30 minutes to be cured to obtain an insulating layer formed of the cured product. The surface of the insulating layer is roughened by immersing it in a swelling solution at 60 ° C. for 5 minutes, immersing it in a roughening solution at 80 ° C. for 15 minutes, and immersing it in a neutralizing solution at 40 ° C. for 5 minutes. Perform processing. Then, a plated conductor layer is formed on the surface of the insulating layer by a semi-additive method to obtain an evaluation substrate. A test is conducted in which this evaluation substrate is passed through a reflow device (“HAS-6116” manufactured by Antomu Japan, Inc.) that reproduces a solder reflow temperature with a peak temperature of 260 ° C. (the reflow temperature profile is IPC / JEDEC J-STD-). Compliant with 020C). When such a test is performed, the swelling of the conductor layer can be suppressed. For example, when the above test is performed on samples of five insulating layers, the number of samples in which swelling occurs can be preferably 2 or less, more preferably zero. As the specific operation of the above-mentioned evaluation of blister resistance, the method described in [Evaluation of blister resistance] of Examples can be adopted.

The present inventor presumes that the mechanism by which the above-mentioned resin composition can achieve excellent blister resistance and process resistance is as follows. However, the technical scope of the present invention is not limited to the following mechanism.

Since the resin composition contains (C) hollow inorganic particles, a hollow portion is formed in the insulating layer formed of the cured product of the resin composition. Since this hollow portion can suppress heat transfer, it is possible to suppress heat intrusion during reflow. Therefore, since the decomposition of the resin due to the heat entering the insulating layer can be suppressed, the generation of gas from the insulating layer can be suppressed. Therefore, it is possible to suppress the conductor layer on the insulating layer from being pushed up by this gas, so that blister can be suppressed.

However, in general, hollow particles having a hollow portion are subject to impact in a process of being dispersed by a dispersion device such as a mixer and are easily broken. Therefore, the conventional resin composition containing hollow particles has low process resistance, and it is difficult to improve both blister resistance and process resistance.

On the other hand, the inorganic composite oxide as the material of the hollow inorganic particles (C) satisfying the requirement (c1) generally has high mechanical strength. Therefore, even if it receives an impact, it is not easily damaged. On the other hand, since the hollow inorganic particles (C) satisfying the requirement (c2) have a small particle shape, when they receive an impact, the impact force should be released in a direction intersecting the radial direction (surface direction, etc.). Can be done. Therefore, the impact force transmitted in the radial direction can be reduced. In general, the outer shell portion of hollow particles is easily cracked by an impact force in the radial direction, and is difficult to crack by an impact force in a direction intersecting the radial direction. Therefore, the hollow inorganic particles (C) are not easily damaged even when subjected to an impact force. Therefore, in the resin composition according to the present embodiment, since the cracking of the hollow inorganic particles (C) can be suppressed, both the blister resistance and the process resistance can be improved.

The cured product of the above-mentioned resin composition can usually have a low dielectric constant. Therefore, by using the above-mentioned resin composition, an insulating layer having a low dielectric constant can be obtained.
In one embodiment, the resin composition is dried and heated at 200 ° C. for 90 minutes to cure to obtain a cured product. The relative permittivity of this cured product can be preferably 3.0 or less, more preferably 2.9 or less, still more preferably 2.8 or less, and particularly preferably 2.6 or less.
The relative permittivity of the cured product was determined by a cavity resonance permittivity method using an analyzer (“HP8632B” manufactured by Agilent Technologies) for an evaluation sample consisting of a cured product having a length of 80 mm, a width of 2 mm, and a thickness of 40 μm. It can be measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. As a specific operation for measuring the relative permittivity of the cured product of the resin composition, the method described in [Measurement of Relative Permittivity Dk] of Examples can be adopted.

The cured product of the above-mentioned resin composition can usually have a small coefficient of linear thermal expansion. Therefore, by using the above-mentioned resin composition, it is possible to obtain an insulating layer that is less likely to warp.
In one embodiment, the resin composition is dried and heated at 200 ° C. for 90 minutes to cure to obtain a cured product. The average linear thermal expansion integer from 25 ° C. to 150 ° C. of the cured product can be preferably 45 ppm / ° C. or lower, more preferably 40 ppm / ° C. or lower, and particularly preferably 38 ppm / ° C. or lower.
The coefficient of linear thermal expansion of the cured product is about 15 mm in length, about 5 mm in width, and 40 μm in thickness. It can be measured by performing an analysis. This measurement can be performed under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. As a specific operation for measuring the linear thermal expansion coefficient of the cured product of the resin composition, the method described in [Evaluation of linear thermal expansion coefficient CTE] of the example can be adopted.

[18. Uses of resin composition]
The above-mentioned resin composition 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). In particular, from the viewpoint of effectively utilizing the excellent blister resistance, the above-mentioned resin composition is a resin for forming the insulating layer for forming a conductor layer (including a rewiring layer) on the insulating layer. It is desirable to use it as a composition (resin composition for forming an insulating layer for forming a conductor layer).

Further, the above-mentioned resin composition forms a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board) and an interlayer insulating layer of a printed wiring board. It can be suitably used as a resin composition (resin composition for forming an interlayer insulating layer of a printed wiring board).

[19. Resin sheet]
The resin sheet according to the embodiment of the present invention includes a support and a resin composition layer provided on the support and containing the above-mentioned resin composition.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be, for example, 5 μm or more, 10 μm or more, and the like.

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 abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonates (hereinafter abbreviated as "PC"), polymethylmethacrylates (hereinafter abbreviated as "PMMA") and other acrylic polymers, cyclic polyolefins, triacetyl celluloses (hereinafter abbreviated as "PMMA"). Examples thereof include "TAC"), polyether sulfide (hereinafter, may be abbreviated as "PES"), polyether ketone, polyimide and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, and the like, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be treated with a matte treatment, a corona treatment, an antistatic treatment, or the like.

Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more types of release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based mold release agent as a main component. "AL-5", "AL-7"; "Lumilar T60" manufactured by Toray Industries, Inc .; "Purex" manufactured by Teijin Ltd.; "Unipeel" 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, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is 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 arbitrary layer include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. The protective film can suppress the adhesion of dust and the like to the surface of the resin composition layer and scratches.

For the resin sheet, for example, a resin varnish containing an organic solvent and a resin composition is prepared, and this 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. By forming it, it can be manufactured.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol and the like. Carbitol solvent; aromatic hydrocarbon solvent such as toluene and xylene; amide solvent 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 carried out 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 depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A 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.

[20. Printed wiring board]
The printed wiring board according to the embodiment of the present invention includes an insulating layer formed of a cured product of the above-mentioned resin composition. Since the insulating layer of this printed wiring board is formed of the cured product of the above resin composition, it is possible to suppress the variation in quality for each product lot due to (C) cracking of hollow inorganic particles, and the conductor layer during reflow can be suppressed. The swelling can be suppressed.

There are no restrictions on the manufacturing method of the printed wiring board. The printed wiring board can be manufactured, for example, by using the above-mentioned resin sheet by a 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 thermally curing the resin composition layer to form an insulating layer.

The "inner layer board" used in the step (I) is a member that becomes a board of a printed wiring board. Examples of the inner layer substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. The inner layer substrate may have a conductor layer on one side or both sides thereof. This conductor layer may be patterned, for example, to function as a circuit. An inner layer board in which a conductor layer is formed as a circuit on one side or both sides of the board may be referred to as an "inner layer circuit board". Further, an intermediate product in which an insulating layer and / or a conductor layer should be further formed when the printed wiring board is manufactured 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 containing built-in components may be used.

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

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

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

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

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

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

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

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

When the support is removed after the step (II), the support may be removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out at any time between IV) and step (V). Above all, from the viewpoint of further suppressing the generation of the hollowed portion, it is preferable to remove the support after the step (III) of drilling the insulating layer. For example, when the support is peeled off after making a hole in the insulating layer by irradiation with a laser beam, it is easy to form a hole having a good shape.

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

Step (IV) is a step of roughening the insulating layer. In step (IV), smear removal is also usually performed. The procedure and conditions of the roughening process are not particularly limited. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent as a roughening liquid, and a neutralization treatment with a neutralizing liquid in this order. The roughening treatment can also be performed by a dry treatment such as plasma treatment or a mechanical treatment such as sandblasting.

The swelling liquid is not particularly limited, and examples thereof include an alkaline solution, a surfactant solution, and the like, and an alkaline solution is preferable. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security Guns P" and "Swelling Dip Security Guns SBU" manufactured by Atotech Japan. Further, one type of swelling liquid may be used alone, or two or more types may be used in combination. 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 to 15 minutes.

The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. In addition, one type of oxidizing agent may be used alone, or two or more types may be used in combination. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact P", "Concentrate Compact CP", and "Dosing Solution Security 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. In addition, one type of neutralizing liquid may be used alone, or two or more types may be used in combination. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more, and the like. The root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more, and the like. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

The step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. 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, from the viewpoint of versatility, cost, ease of patterning, etc. for forming the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or a nickel-chromium alloy, copper. -Alloy layers of nickel alloys and copper-titanium alloys; are preferred. Further, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or an alloy layer of a nickel-chromium alloy; is more preferable, and a single metal layer of copper is even more preferable.

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

The thickness of the conductor layer depends on the design of the desired 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. Above all, from the viewpoint of ease of production, it is preferable to form by the semi-additive method.

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

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

[21. Semiconductor device]
The semiconductor device according to the 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 in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

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

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

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

[Measuring method of average particle size of inorganic particles]
The average particle size of the inorganic particles was measured by the following method.
100 mg of inorganic particles 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 wavelengths of the light sources used were blue and red, and the particle size distribution of the inorganic particles was measured by the flow cell method on a volume basis. From the obtained particle size distribution, the average particle size of the inorganic particles was calculated as the median diameter.

[Measurement method of porosity of inorganic particles]
The porosity of the inorganic particles was measured by the following method.
The density of the inorganic particles was measured using a true density measuring device (“ULTRAPYCNOMETER1000” manufactured by QUANTACHROME). In this measurement, nitrogen was used as the measurement gas. Then, using the measured density and the material density of the inorganic material (aluminosilicate or silica) forming the inorganic particles, the porosity of the inorganic particles was measured according to the above formula (X). In formula (X), the substance density of silica as an inorganic material was 2.2 g / cm ³ , and the substance density of aluminosilicate used in Examples and Comparative Examples was 2.5 g · cm ³ .
Pore ratio (% by volume) = {1- (measured density [g / cm ³ ] / material density of inorganic material [g / cm ³ ])} x 100 (X)

[Synthesis example 1. Production of Hollow Silica Particles 1]
Hollow silica particles 1 were synthesized according to the description of Japanese Patent No. 5940188. The average particle size of the obtained hollow silica particles 1 was 3 μm, and the porosity was 20% by volume.

[Synthesis example 2. Production of Hollow Silica Particles 2]
Hollow silica particles 2 were synthesized in the same manner as in Synthesis Example 1. The average particle size of the obtained hollow silica particles 2 was 2.7 μm, and the porosity was 10% by volume.

[Example 1]
7 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269), 7 parts of liquid 1,4-glycidylcyclohexane ("ZX1658" manufactured by Nittetsu Chemical & Materials Co., Ltd., epoxy equivalent of about 135), bi 10 parts of xylenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Co., Ltd., active group equivalent of about 223, non-volatile component 65% by mass) 60 parts of toluene solution), 3 parts of triazine skeleton-containing phenolic curing agent (DIC's "LA-3018-50P", hydroxyl group equivalent of about 151, 2-methoxypropanol solution of 50% non-volatile component), phenoxy resin (Mitsubishi Chemicals, Inc.) 8 parts of "YX7553BH30" manufactured by YX7553BH30, a 1: 1 solution of MEK and cyclohexanone having a non-volatile component of 30% by mass, a carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., an active group equivalent of about 216, a toluene solution having a non-volatile component of 50% by mass). ) 10 parts, hollow aluminum nosilicate particles (“MG-005” manufactured by Pacific Cement Co., Ltd., average particle size 1.6 μm, pore ratio 80% by volume, specific surface area 6.1 m ² / g) 20 parts, curing accelerator (4) -Dimethylaminopyridine (DMAP), 5 parts by mass of a non-volatile component MEK solution), 15 parts of methyl ethyl ketone, and 10 parts of cyclohexanone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

As a support, a polyethylene terephthalate film with a mold release treatment (“AL5” manufactured by Lintec Corporation, thickness 38 μm) was prepared. A resin varnish was uniformly applied onto the release surface of the support so that the thickness of the resin composition layer after drying was 30 μm, and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 6 minutes. A resin sheet was produced.

[Example 2]
One part of rubber particles (“Staffyloid AC3816N” manufactured by Ganz Kasei Co., Ltd.) as an organic filler was added to the material of the resin varnish. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Example 3]
Phosphorus flame retardant ("HCA-HQ" manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide ) Added two copies. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Example 4]
To the material of the resin varnish, 4 parts of a phosphazen compound (a 50% cyclohexanone solution of a non-volatile component of "SPS-100" manufactured by Otsuka Chemical Co., Ltd.) was added. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Example 5]
The amount of the active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, toluene solution of 65% by mass of non-volatile component) was changed from 60 parts to 55 parts. Further, 5 parts of a benzoxazine-based curing agent (benzoxazine monomer "Pd" manufactured by Shikoku Kasei Co., Ltd., active group equivalent 217, MEK solution having a non-volatile component of 60% by mass) was added to the material of the resin varnish. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Example 6]
The amount of the curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having 5% by mass of the non-volatile component) was changed from 5 parts to 3 parts. Further, 0.1 part of a curing accelerator (“1B2PZ” manufactured by Shikoku Chemicals Corporation, 1-benzyl-2-phenylimidazole) was added to the material of the resin varnish. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Example 7]
20 parts of hollow aluminosilicate particles ("MG-005" manufactured by Taiheiyo Cement Co., Ltd., average particle size 1.6 μm, porosity 80% by volume) are surfaced with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.). The treated hollow aluminosilicate particles (“MG-005” manufactured by Taiheiyo Cement Co., Ltd., average particle size 1.6 μm, porosity 80% by volume) were changed to 20 parts. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Example 8]
10 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269), 10 parts of bixylenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), bisphenol AF type epoxy resin ( Mitsubishi Chemical "YL7760", epoxy equivalent about 238) 10 parts, bisphenol A type epoxy resin (Mitsubishi Chemical "828EL", epoxy equivalent about 180) 10 parts, active ester curing agent (DIC "HPC-" 8000-65T ”, active group equivalent about 223, non-volatile component 65% by mass toluene solution) 50 parts, triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent about 151, non-volatile component 50 2 parts of 2-methoxypropanol solution), 8 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 1: 1 solution of MEK and cyclohexanone of 30% by mass of non-volatile component), carbodiimide compound ("V-" manufactured by Nisshinbo Chemical Co., Ltd.) 03 ”, active group equivalent of about 216, non-volatile component 50% by mass toluene solution) 5 parts, oligophenylene ether styrene resin (Mitsubishi Gas Chemicals Co., Ltd.“ OPE-2St 1200 ”, non-volatile component 72% by mass toluene solution) 10 Part, 0.2 part of dicumyl epoxy ("Park Mill D" manufactured by Nichiyu Co., Ltd.), curing accelerator (2-phenyl-4-methylimidazole (2P4MZ) manufactured by Shikoku Kasei Kogyo Co., Ltd.), MEK with 5% by mass of non-volatile component 5 parts of solution), 20 parts of hollow epoxynosilicate particles (“MG-005” manufactured by Pacific Cement Co., Ltd., average particle size 1.6 μm, pore ratio 80% by volume), 15 parts of methyl ethyl ketone, and 10 parts of cyclohexanone were mixed. A resin varnish was prepared by uniformly dispersing it with a high-speed rotating mixer.

As a support, a polyethylene terephthalate film with a mold release treatment (“AL5” manufactured by Lintec Corporation, thickness 38 μm) was prepared. A resin varnish is uniformly applied onto the mold release surface so that the thickness of the resin composition layer after drying is 30 μm, and the resin sheet is dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a resin sheet. Made.

[Example 9]
10 parts of bixirenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent about 185), 20 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "828EL", epoxy equivalent about 180), naphthalene type epoxy resin (Japan) Iron Chemical & Materials "ESN475V", epoxy equivalent about 332) 10 parts, naphthylene ether type epoxy resin (DIC "HP-6000", epoxy equivalent 250) 20 parts, active ester curing agent (DIC) "HPC-8000-65T", active group equivalent of about 223, non-volatile component 65% by mass toluene solution) 30 parts, epoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", non-volatile component 30% by mass MEK and cyclohexanone 1: 1 Solution) 8 parts, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide ("BMI-70" manufactured by Keiai Kasei Co., Ltd.) 12 parts, hollow aluminum nosilicate particles (Pacific cement) Spherical silica (average grain) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 8 parts of "MG-005" manufactured by the company, average particle size 1.6 μm, pore ratio 80% by volume). Diameter 0.5 μm, pore ratio 0% by volume, 50 parts of Admatex “SO-C2”), 5 parts of curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution of 5% by mass of non-volatile component), 15 parts of methyl ethyl ketone and 10 parts of cyclohexanone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

As a support, a polyethylene terephthalate film with a mold release treatment (“AL5” manufactured by Lintec Corporation, thickness 38 μm) was prepared. A resin varnish is uniformly applied onto the mold release surface so that the thickness of the resin composition layer after drying is 30 μm, and the resin sheet is dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a resin sheet. Made.

[Example 10]
10 parts of bixirenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent of about 185), 20 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "828EL", epoxy equivalent of about 180), naphthalene type epoxy resin (Japan) Iron Chemical & Materials "ESN475V", epoxy equivalent about 332) 10 parts, naphthylene ether type epoxy resin (DIC "HP-6000", epoxy equivalent 250) 20 parts, active ester curing agent (DIC) "HPC-8000-65T", active group equivalent of about 223, non-volatile component 65% by mass toluene solution) 20 parts, epoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", non-volatile component 30% by mass MEK and cyclohexanone 1: 1 8 parts of solution), 10 parts of bisphenol A dicyanate ("Primaset BADCy" manufactured by Ronza Japan, cyanate equivalent of about 139), prepolymer of bisphenol A dicyanate ("Primaset BA230S75" manufactured by Ronza Japan, cyanate equivalent of about 232, non-volatile component 75) 10 parts by mass% MEK solution), 85 parts of hollow aluminum nosilicate particles (“MG-005” manufactured by Pacific Cement Co., Ltd., average particle size 1.6 μm, pore ratio 80% by volume), cobalt (III) acetylacetonate (Tokyo) Kasei Co., Ltd., 5 parts of CO (III) AcAc 1% by mass MEK solution), 3 parts of curing accelerator (4-dimethylaminopyridine (DMAP), 5 parts by mass of non-volatile component MEK solution), 60 parts of methyl ethyl ketone , And 40 parts of cyclohexanone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

As a support, a polyethylene terephthalate film with a mold release treatment (“AL5” manufactured by Lintec Corporation, thickness 38 μm) was prepared. A resin varnish is uniformly applied onto the mold release surface so that the thickness of the resin composition layer after drying is 30 μm, and the resin sheet is dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 6 minutes to obtain a resin sheet. Made.

[Comparative Example 1]
20 parts of hollow aluminosilicate particles (“MG-005” manufactured by Pacific Cement Co., Ltd., average particle size 1.6 μm, porosity 80% by volume) were produced in Synthetic Example 1 with hollow silica particles 1 (average particle size 3 μm, empty). Porosity 20% by volume) was changed to 60 parts. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 2]
20 parts of hollow aluminosilicate particles (“MG-005” manufactured by Pacific Cement Co., Ltd., average particle size 1.6 μm, porosity 80% by volume) were produced in Synthetic Example 2 with hollow silica particles 2 (average particle size 2.7 μm). , Porosity 10% by volume) was changed to 70 parts. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 3]
20 parts of hollow aluminosilicate particles (“MG-005” manufactured by Pacific Cement Co., Ltd., average particle size 1.6 μm, porosity 80% by volume) are surfaced with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.). The treated spherical silica (average particle size 0.5 μm, porosity 0% by volume, “SO-C2” manufactured by Admatex) was changed to 75 parts. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 4]
20 parts of hollow aluminosilicate particles (“MG-005” manufactured by Pacific Cement Co., Ltd., average particle size 1.6 μm, porosity 80% by volume), polytetrafluoroethylene (PTFE) particles (“Lubron L-” manufactured by Daikin Industries, Ltd.) 2 ”, 25 parts with an average particle size of 3 μm), and spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (average particle size 0.5 μm, porosity 0% by volume, Changed to a combination of 50 copies of "SO-C2" manufactured by Admatex. Except for the above items, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Preparation of cured product for evaluation]
A glass cloth base material epoxy resin double-sided copper-clad laminate (Panasonic "R5715ES") on the release agent-treated PET film (Lintec "501010", thickness 38 μm, 240 mm square), which has been treated with a mold release agent. (Thickness 0.7 mm, 255 mm square) were overlapped, and the four sides were fixed with polyimide adhesive tape (width 10 mm). This PET film may be hereinafter referred to as "fixed PET film".

The resin varnishes obtained in Examples and Comparative Examples were applied onto the mold release-treated surface of the above-mentioned fixed PET film using a die coater so that the thickness of the resin composition layer after drying was 40 μm, and 80 The resin sheet was obtained by drying at ° C. to 120 ° C. (average 100 ° C.) for 10 minutes.

The resin sheet was then placed in an oven at 200 ° C. and then heated for 90 minutes to thermoset the resin composition layer.

After thermosetting, the polyimide adhesive tape was peeled off, the glass cloth base material epoxy resin double-sided copper-clad laminate was peeled off, and the PET film (“501010” manufactured by Lintec Corporation) was peeled off to obtain a sheet-shaped cured product. The obtained cured product is called an "evaluation cured product".

[Measurement of relative permittivity Dk]
The cured product for evaluation was cut to obtain an evaluation sample having a length of 80 mm and a width of 2 mm. The relative permittivity of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an analyzer (“HP8632B” manufactured by Agilent Technologies). Measurements were made on the two test pieces, and the average value was calculated.

[Evaluation of linear thermal expansion coefficient CTE]
The cured product for evaluation was cut to obtain a test piece having a length of about 15 mm and a width of about 5 mm. This test piece was subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). After the test piece was attached to the apparatus, measurements were made twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the average linear thermal expansion rate from 25 ° C to 150 ° C was calculated.

[Evaluation of elastic modulus YM]
The cured product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec, and the elastic modulus at 25 ° C. was determined. The measurement was carried out in accordance with JIS K7127. This operation was performed three times, and the average value was calculated (unit: GPa).

[Process resistance evaluation of hollow particles]
The resin varnishes obtained in Examples and Comparative Examples were put into a homomixer (“TK Agi-Homo-Mixer” manufactured by Primix Corporation). This homomixer was rotated at 7000 rpm for 30 minutes to obtain a sample varnish for process resistance evaluation.

Except for using the sample varnish thus obtained in place of the resin varnish, the same operation as in the above-mentioned [Preparation of cured product for evaluation] was performed to prepare a cured product for evaluation. A cross-sectional observation of this cured product for evaluation was carried out using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Inc.). Specifically, a cross section in a direction perpendicular to the surface of the cured product for evaluation was cut out by a FIB (focused ion beam), and a cross-section SEM image (observation width 30 μm, observation magnification 9,000 times) was obtained. Further, in the above-mentioned cross-sectional observation, SEM images of five randomly selected cross-sections were obtained for each evaluation cured product. In the acquired cross-sectional SEM image, the process resistance of the particles showing cracks was judged to be “x”, and the process resistance of those not seen was judged to be “〇”.

[Evaluation of blister resistance]
(1) Lamination of resin sheet:
The resin sheets obtained in Examples and Comparative Examples were subjected to a glass cloth base material epoxy resin double-sided copper-clad laminate (Panasonic "R5715ES") using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.). , 0.7 mm thick, 255 mm square), laminated so that the resin composition layer is in contact with both sides. This laminating was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(2) Curing of resin composition layer:
The support was peeled off from the laminated resin sheet. Then, the resin composition layer was heat-cured at 180 ° C. for 30 minutes to form an insulating layer. As a result, a "laminated substrate A" having an insulating layer, a laminated board, and an insulating layer in this order was obtained.

(3) Roughening treatment:
The surface of the insulating layer of the produced laminated substrate A is immersed in a swelling solution (Atotech Japan's diethylene glycol monobutyl ether-containing swelling dip seculigand P) at 60 ° C. for 5 minutes, and then a roughening solution (Atotech Japan's company). Immerse in Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 15 minutes, and then a neutralizing solution (Atotech Japan's Reduction Shorusin Security). It was immersed in Gantt P) at 40 ° C. for 5 minutes to obtain "roughened substrate B".

(4) Plating by semi-additive method:
In order to form a circuit on the surface of the insulating layer, the roughened substrate B was immersed in an electroless plating solution containing PdCl ₂ , and then immersed in an electroless copper plating solution. After heating at 150 ° C. for 30 minutes for annealing treatment, 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 30 ± 5 μm. Next, the annealing treatment was performed at 180 ° C. for 60 minutes. As a result, an "evaluation substrate C" as a circuit board having a conductor layer on the insulating layer was obtained.

(5) Evaluation of blisters in the reflow process:
The evaluation substrate C was cut to obtain a small piece of 100 mm × 50 mm. This small piece was passed through a reflow device (“HAS-6116” manufactured by Antomu Japan, Inc.) that reproduces the solder reflow temperature with a peak temperature of 260 ° C. 5 times (the reflow temperature profile is IPC / JEDEC J-STD-020C). Compliant with). The above test was performed with 5 small pieces, and the small pieces after the test were visually observed. As a result of visual observation, the blister resistance was judged to be "x" although there were abnormalities such as blisters in the conductor layer in three or more small pieces. In addition, the blister resistance was judged to be "Δ" although there were abnormalities such as blisters in the conductor layer with one or two small pieces. Furthermore, the blister resistance of all the small pieces was judged to be "○", although there was no abnormality at all.

[result]
The results of Examples and Comparative Examples are shown in the table below. In the table below, the "liquid component ratio" represents the mass ratio of the liquid component to 100% by mass of the non-volatile component of the resin composition. Among the non-volatile components of the resin varnish used in the above Examples and Comparative Examples, the liquid components are liquid 1,4-glycidylcyclohexane (“ZX1658” manufactured by Nittetsu Chemical & Materials Co., Ltd.) and bisphenol A type epoxy resin (Mitsubishi). "828EL" manufactured by Kagaku Co., Ltd.) and a curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd.) are applicable. Further, in the table below, the numerical values in the column of the components used for preparing the resin composition represent the blending amount (non-volatile content conversion) of each component.

In the examples, it has been confirmed that even when the components (D) to (L) are not contained, the same results as those in the above-mentioned examples are obtained, although the degree is different.

Claims (10)

A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) hollow inorganic particles.
(C) The hollow inorganic particles satisfy at least one of the following requirements (c1) and (c2).
A resin composition having a cured product obtained by heating the resin composition at 200 ° C. for 90 minutes and having an average linear thermal expansion integer of 42 ppm / ° C. or less from 25 ° C. to 150 ° C.
(C1): (C) Hollow inorganic particles are formed of an inorganic composite oxide.
(C2): The porosity of the hollow inorganic particles (C) is 25% by volume or more, and the average particle size of the hollow inorganic particles (C) is 5.0 μm or less. (C) The resin composition according to claim 1, wherein the amount of the hollow inorganic particles is 50% by mass or less with respect to 100% by mass of the non-volatile component in the resin composition. (C) The resin composition according to claim 1 or 2, wherein the hollow inorganic particles are formed of aluminosilicate. The resin composition according to any one of claims 1 to 3, wherein in the requirement (c2), the average particle size of the hollow inorganic particles (C) is 2.5 μm or less. The resin composition according to any one of claims 1 to 4, wherein the component liquid at 20 ° C. is contained in an amount of 3% by mass or more with respect to 100% by mass of the non-volatile component in the resin composition. The resin composition according to any one of claims 1 to 5, which contains (D) a thermoplastic resin of 0.1% by mass or more and 15% by mass or less with respect to 100% by mass of the non-volatile component of the resin composition. The resin composition according to any one of claims 1 to 6 , which is used for forming an insulating layer for forming a conductor layer. With the support,
A resin sheet provided on a support and comprising a resin composition layer containing the resin composition according to any one of claims 1 to 7 . A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 7 . A semiconductor device including the printed wiring board according to claim 9 .