JP2020033568A - Resin composition and adhesive film - Google Patents

Abstract

To provide a resin composition that can give an insulating layer being excellent in all properties of dielectric loss tangent, thermal expansion coefficient, breaking point elongation, surface roughness and peel strength in the production of a printed wiring board.SOLUTION: A resin composition has (A) epoxy resin, (B) active ester compound, (C) carbodiimide compound, (D) thermoplastic resin and (E) inorganic filler, the content of (E) component being 40 mass% or more when a nonvolatile component in the resin composition is 100 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Further, the present invention relates to an adhesive film, a printed wiring board, and a semiconductor device using the resin composition.

  As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductive layers are alternately stacked is known. In a manufacturing method using a build-up method, generally, an insulating layer is formed by curing a resin composition. For example, Patent Literature 1 discloses a technique in which a resin composition containing an epoxy resin, an active ester compound, and a carbodiimide compound is cured to form a low dielectric loss tangent insulating layer.

  The number of laminations due to the build-up of printed wiring boards has tended to increase due to the recent tendency to be light and thin, but cracks and circuit distortion due to the difference in thermal expansion between the insulating layer and the conductor layer due to the increase in the number of laminations Is a problem. As a technique for suppressing such problems of cracks and circuit distortion, for example, in Patent Document 2, by increasing the content of an inorganic filler in a resin composition, the coefficient of thermal expansion of an insulating layer to be formed is suppressed to be low. Techniques are disclosed.

JP 2006-335834 A JP 2010-202865 A

  The inventors of the present invention have found that, when manufacturing a printed wiring board, a high content of an inorganic filler is added to the resin composition described in Patent Document 1 in order to form an insulating layer having a low dielectric loss tangent and a low coefficient of thermal expansion. Tried. The resulting resin composition may result in an insulating layer exhibiting the expected dielectric loss tangent and coefficient of thermal expansion, but may result in an insulating layer having poor properties such as elongation at break, surface roughness, and peel strength. The present inventors have found.

  An object of the present invention is to provide a resin composition capable of providing an insulating layer that is excellent in any of the properties of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength when manufacturing a printed wiring board. As an issue.

  The present inventors have conducted intensive studies on the above problems, and as a result, have found that the following specific resin composition can solve the above problems, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin, and (E) an inorganic filler, wherein the content of the component (E) is A resin composition, which has a content of 40% by mass or more when the nonvolatile component in the composition is 100% by mass.
[2] The resin composition according to [1], wherein the component (D) has a weight average molecular weight of 10,000 to 200,000.
[3] The component (D) is a thermoplastic resin having a functional group containing one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom or a carbon-carbon double bond. The resin composition according to [1] or [2].
[4] The component (D) is a hydroxyl group, a carboxy group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, a diimide group, The resin composition according to any one of [1] to [3], which is a thermoplastic resin having one or more functional groups selected from the group consisting of an alkenyl group, an allene group, and a ketene group.
[5] The component (D) is at least one thermoplastic resin selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, a vinyl resin containing an acid anhydride group, a polyimide resin, a polyamideimide resin, and a styrene-based elastomer resin. The resin composition according to any one of [1] to [4].
[6] The resin composition according to any one of [1] to [5], wherein the component (C) has a weight average molecular weight of 500 to 5,000.
[7] The resin composition according to any one of [1] to [6], wherein the component (C) has an NCO content of 5% by mass or less.
[8] The resin composition according to any one of [1] to [7], wherein the content of the component (E) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. .
[9] The resin composition according to any one of [1] to [8], wherein the component (E) has an average particle size of 0.01 μm to 3 μm.
[10] The resin composition according to any one of [1] to [9], wherein the component (E) is silica.
[11] The resin composition according to any one of [1] to [10], further comprising (F) a curing accelerator.
[12] The resin composition according to [11], wherein the component (F) is 4-dimethylaminopyridine or 1-benzyl-2-phenylimidazole.
[13] Any of [1] to [12], wherein the resin composition is cured to form an insulating layer, and an arithmetic average roughness (Ra) after the surface of the insulating layer is roughened is 140 nm or less. A resin composition according to any one of the above.
[14] The resin composition according to any one of [1] to [13], wherein the cured product of the resin composition has an elongation at break of 2% or more.
[15] The resin composition according to any one of [1] to [14], wherein the cured product of the resin composition has a glass transition temperature (Tg) of 165 ° C or higher.
[16] An adhesive film comprising a support and a layer of the resin composition according to any one of [1] to [15] bonded to the support.
[17] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [15].
[18] A semiconductor device including the printed wiring board according to [17].

  According to the present invention, there is provided a resin composition capable of providing an insulating layer having excellent properties in any of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness, and peel strength when manufacturing a printed wiring board. can do.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments.

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin, and (E) an inorganic filler, and contains (E) a component. Is 40% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

  When a high content of (E) an inorganic filler is added to a resin composition containing (A) an epoxy resin, (B) an active ester compound and (C) a carbodiimide compound, the resulting resin composition has a low dielectric constant. The present inventors have found that while providing an insulating layer having a tangent and a low coefficient of thermal expansion, the insulating layer may be inferior in properties such as elongation at break, surface roughness, and peel strength. The resin composition of the present invention further comprises (D) a thermoplastic resin, thereby providing an insulating layer having excellent elongation at break, surface roughness and peel strength while maintaining a low dielectric loss tangent and a low coefficient of thermal expansion. It is possible to do that. In this regard, even if the thermoplastic resin (D) is added to the resin composition (B) containing no active ester compound, the desired elongation at break, surface roughness and peel strength are not achieved. Further, even if the thermoplastic resin (D) is added to the resin composition (C) containing no carbodiimide compound, the desired elongation at break, surface roughness and peel strength are not achieved. When the thermoplastic resin (D) is added to the resin composition (E) having a low inorganic filler content, the desired dielectric loss tangent and thermal expansion coefficient are not achieved in the first place. These are clearly understood from the results of the comparative examples described later. As described above, the effect of the resin composition of the present invention is such that, in addition to (A) the epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin, and a certain amount or more of ( E) It is an effect brought specifically and synergistically by using an inorganic filler in combination.

  Hereinafter, each component contained in the resin composition of the present invention will be described.

<(A) Epoxy resin>
The resin composition of the present invention contains an epoxy resin as the component (A).

  As the epoxy resin, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolak epoxy resin, Phenol novolak type epoxy resin, alicyclic epoxy resin having ester skeleton, 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 Resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy Alicyclic, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. One epoxy resin may be used alone, or two or more epoxy resins may be used in combination.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C. (hereinafter, referred to as “liquid epoxy resin”), and having three or more epoxy groups in one molecule, It is preferable to include a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, a resin composition having excellent flexibility can be obtained. Further, the breaking strength of the cured product of the resin composition is also improved.

  Examples of the liquid epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, phenol novolak epoxy resin, and alicyclic epoxy resin having an ester skeleton. And an epoxy resin having a butadiene structure are preferred, and bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, alicyclic epoxy resin having an ester skeleton, and naphthalene epoxy resin are more preferred, and bisphenol A Epoxy resin and bisphenol AF epoxy resin are more preferred, and bisphenol AF epoxy resin is particularly preferred from the viewpoint of excellent balance of physical properties of the cured product. . Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US” and “jER828EL” manufactured by Mitsubishi Chemical Corporation. (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “ZX1059” (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” manufactured by Daicel Corporation ] (Ester skeleton Alicyclic epoxy resin) having, "PB-3600" (epoxy resin having a butadiene structure) and the like. These may be used alone or in combination of two or more.

  Examples of the solid epoxy resin include a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferred. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (naphthalene-type tetrafunctional epoxy resin), “N-690” (cresol novolac-type epoxy resin), and “HP-4700” manufactured by DIC Corporation. N-695 "(cresol novolak type epoxy resin)," HP-7200 "(dicyclopentadiene type epoxy resin)," EXA7311 "," EXA7311-G3 "," EXA7311-G4 "," EXA7311-G4S "," HP6000 " (Naphthylene ether type epoxy resin), Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", “NC3000L”, “NC3100” (biphenyl "ESN475V" (naphthol type epoxy resin) and "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation, "YX4000H" and "YL6121" (biphenyl type) manufactured by Mitsubishi Chemical Corporation. Epoxy resin), "YX4000HK" (bixylenol type epoxy resin (biphenyl type epoxy resin)), "YX8800" (anthracene type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin), etc. Is mentioned.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1: 8 by mass. preferable. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) moderate adhesiveness is obtained when used in the form of an adhesive film, and ii) when used in the form of an adhesive film. And iii) a cured product having a sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1: 7 by mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 6 is still more preferable.

The content of the epoxy resin in the resin composition is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably, it is 10% by mass to 35% by mass or 10% by mass to 30% by mass.
In the present invention, the content of each component in the resin composition is a value when the nonvolatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, more preferably from 50 to 3,000, further preferably from 80 to 2,000, and still more preferably from 110 to 1,000. When the content falls within this range, the crosslinked density of the cured product becomes sufficient and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236 and is the mass of a resin containing one equivalent of an epoxy group.
The weight average molecular weight of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, and still more preferably from 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(B) Active ester compound>
The resin composition of the present invention contains an active ester compound as the component (B).

  The active ester compound is a compound having one or more active ester groups in one molecule, and is used in combination with (C) a carbodiimide compound described below, (D) a thermoplastic resin, and a certain amount or more of (E) an inorganic filler. By using this, it is possible to provide an insulating layer that is excellent in any of the properties of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness, and peel strength.

  As the active ester compound, a compound having two or more active ester groups in one molecule is preferable. For example, a reaction of a phenol ester, a thiophenol ester, an N-hydroxyamine ester, an ester of a heterocyclic hydroxy compound, or the like. A compound having two or more highly active ester groups in one molecule is preferably used. The active ester compound may be used alone or in combination of two or more.

  From the viewpoint of improving heat resistance, an active ester compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from a phenol compound, a naphthol compound and a thiol compound is more preferable, and a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group are preferred. Is more preferably an aromatic compound having two or more active ester groups in one molecule, and a carboxylic acid compound having at least two or more carboxy groups in one molecule, and a phenolic hydroxyl group. An aromatic compound obtained by reacting an aromatic compound with an aromatic compound, and more preferably an aromatic compound having two or more active ester groups in one molecule. The active ester compound may be linear or branched. Further, if the carboxylic acid compound having at least two or more carboxy groups in one molecule is a compound containing an aliphatic chain, compatibility with the resin composition can be increased, and if the compound has an aromatic ring, Heat resistance can be increased.

  Examples of the carboxylic acid compound include an aliphatic carboxylic acid having 1 to 20 (preferably 2 to 10, more preferably 2 to 8) carbon atoms and an aromatic carboxylic acid having 7 to 20 (preferably 7 to 10) carbon atoms. Carboxylic acids. Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, and itaconic acid. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Above all, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable.

  The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid and thiobenzoic acid.

  Examples of the phenol compound include a phenol compound having 6 to 40 (preferably 6 to 30, more preferably 6 to 23, and still more preferably 6 to 22) carbon atoms. Preferred specific examples thereof include hydroquinone, Resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene-type diphenol. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 may be used.

  The naphthol compound includes, for example, a naphthol compound having 10 to 40 (preferably 10 to 30, more preferably 10 to 20) carbon atoms, and preferable specific examples thereof include α-naphthol, β-naphthol, , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. As the naphthol compound, naphthol novolak may be used.

  Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol, phenol novolak, phosphorus-containing oligomers having a phenolic hydroxyl group are preferred, and catechol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydride Roxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol, phenol novolak, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, , 6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenol, phenol novolak, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, phenol Rac, a phosphorus atom-containing oligomer having a phenolic hydroxyl group is even more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, and phosphorus having a phenolic hydroxyl group Atom-containing oligomers are particularly preferred, and dicyclopentadiene-type diphenols are particularly preferred.

  The thiol compound is not particularly restricted but includes, for example, benzenedithiol, triazinedithiol and the like.

  Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak, and a benzoylated product of phenol novolak. Active ester compounds, active ester compounds obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group, include active ester compounds containing a dicyclopentadiene-type diphenol structure, and naphthalene structures among others An active ester compound, an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group is more preferable. In the present invention, the “dicyclopentadiene-type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  As the active ester compound having a dicyclopentadiene-type diphenol structure, more specifically, a compound represented by the following formula (1) is exemplified.

（式中、Ｒはフェニル基又はナフチル基であり、ｋは０又は１を表し、ｎは繰り返し単位の平均数で０．０５〜２．５である。）

(In the formula, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n is an average number of repeating units of 0.05 to 2.5.)

  From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.

  As the active ester compound, an active ester compound disclosed in JP-A-2004-277460 or JP-A-2013-40270 may be used, or a commercially available active ester compound may be used. Examples of commercially available active ester compounds include, for example, active ester compounds having a dicyclopentadiene-type diphenol structure, such as EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation), and an activity having a naphthalene structure. EXB9416-70BK (manufactured by DIC) as an ester compound, DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolak, and YLH1026 (manufactured by Mitsubishi Chemical) as an active ester compound containing a benzoylated phenol novolak EXB9050L-62M (DIC Corporation) as a phosphorus atom-containing active ester compound.

  In combination with (C) a carbodiimide compound described below, (D) a thermoplastic resin, and a certain amount or more of (E) an inorganic filler, dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength are determined. The content of the active ester compound in the resin composition is preferably 1% by mass or more from the viewpoint of obtaining an insulating layer excellent in any of the properties, particularly, from the viewpoint of obtaining an insulating layer having low surface roughness and high peel strength. 3% by mass or more is more preferable, and 5% by mass or more is further preferable. The upper limit of the content of the active ester compound is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

  Further, when the number of epoxy groups of (A) epoxy resin is 1, from the viewpoint of obtaining an insulating layer having good mechanical strength, the number of reactive groups of (B) active ester compound is preferably from 0.2 to 2, and from 0.3 to 0.3. -1.5 is more preferable, and 0.35-1 is still more preferable. Here, the “number of epoxy groups in the epoxy resin” is a value obtained by dividing the mass of the solid content of each epoxy resin present in the resin composition by the epoxy equivalent and summing the values for all epoxy resins. Further, "reactive group" means a functional group capable of reacting with an epoxy group, and "the number of reactive groups of the active ester compound" means the solid content mass of the active ester compound present in the resin composition. It is the total value of all values divided by the reactive group equivalent.

<(C) Carbodiimide compound>
The resin composition of the present invention contains a carbodiimide compound as the component (C).

  The carbodiimide compound is a compound having one or more carbodiimide groups (-N = C = N-) in one molecule, and includes the above-mentioned (B) active ester compound, (D) a thermoplastic resin described later, and a certain amount or more. When used in combination with the inorganic filler (E), an insulating layer having excellent properties such as dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength can be obtained. As the carbodiimide compound, a compound having two or more carbodiimide groups in one molecule is preferable. The carbodiimide compounds may be used alone or in a combination of two or more.

  In one embodiment, the carbodiimide compound contained in the resin composition of the present invention contains a structural unit represented by the following formula (2).

（式中、Ｘは、アルキレン基、シクロアルキレン基又はアリーレン基を表し、これらは置換基を有していてもよい。ｐは１〜５の整数を表す。Ｘが複数存在する場合、それらは同一でも相異なってもよい。＊は結合手を表す。）

(In the formula, X represents an alkylene group, a cycloalkylene group or an arylene group, which may have a substituent. P represents an integer of 1 to 5. When a plurality of Xs are present, they are They may be the same or different. * Represents a bond.)

  The number of carbon atoms of the alkylene group represented by X is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms does not include the number of carbon atoms of the substituent. Preferable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

  The number of carbon atoms of the cycloalkylene group represented by X is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. The number of carbon atoms does not include the number of carbon atoms of the substituent. Preferable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

  The arylene group represented by X is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms of the arylene group is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and still more preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Preferable examples of the arylene group include a phenylene group, a naphthylene group and an anthracenylene group.

  In combination with (B) an active ester compound, (D) a thermoplastic resin and a certain amount or more of (E) an inorganic filler, dielectric tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength are further improved. From the viewpoint of realizing an excellent insulating layer, X is preferably an alkylene group or a cycloalkylene group, and these may have a substituent.

The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. Examples of the substituent include, but are not particularly limited to, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group. Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group and the alkoxy group used as the substituent may be linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 10. 6, 1-4, or 1-3. The number of carbon atoms of the cycloalkyl group and the cycloalkyloxy group used as the substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is preferably 6 to 24, more preferably 6 to 18, and still more preferably. Is 6 to 14, and even more preferably 6 to 10. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and still more preferably 6 to 10. The acyl group used as a substituent refers to a group represented by the formula: —C (＝ O) —R ¹ (wherein, R ¹ represents an alkyl group or an aryl group). The alkyl group represented by R ¹ may be linear or branched, and preferably has 1 to 20, more preferably 1 to 10, more preferably 1 to 6, carbon atoms. 1-4, or 1-3. The aryl group represented by R ¹ preferably has 6 to 24 carbon atoms, more preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. Acyloxy group used as a substituent of the formula: (wherein, ^{R 1} represents the same meaning as above.) -O-C (= O ) group represented by -R ¹ refers. Among them, as the substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

  In the formula (2), p represents an integer of 1 to 5. In combination with (B) an active ester compound, (D) a thermoplastic resin and a certain amount or more of (E) an inorganic filler, dielectric tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength are further improved. From the viewpoint of realizing an excellent insulating layer, p is preferably 1 to 4, more preferably 2 to 4, and further preferably 2 or 3.

  In the formula (2), when a plurality of Xs are present, they may be the same or different. In a preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

  In a preferred embodiment, the carbodiimide compound is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, when the mass of the entire molecule of the carbodiimide compound is 100% by mass. More preferably, at least 80% by mass or at least 90% by mass contains the structural unit represented by the formula (2). The carbodiimide compound may consist essentially of the structural unit represented by the formula (2) except for the terminal structure. Although the terminal structure of the carbodiimide compound is not particularly limited, examples thereof include an alkyl group, a cycloalkyl group, and an aryl group, and these may have a substituent. The alkyl group, cycloalkyl group and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group and aryl group described for the substituent which the group represented by X may have. Further, the substituent that the group used as the terminal structure may have may be the same as the substituent that the group represented by X may have.

  From the viewpoint of suppressing the generation of outgas when the resin composition is cured, the weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and still more preferably 800 or more. Particularly preferably, it is 900 or more or 1000 or more. In addition, from the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5000 or less, more preferably 4500 or less, still more preferably 4000 or less, still more preferably 3500 or less, and particularly preferably 3000 or less. It is. The weight average molecular weight of the carbodiimide compound can be measured, for example, by gel permeation chromatography (GPC) method (in terms of polystyrene).

  In some cases, the carbodiimide compound contains an isocyanate group (-N = C = O) in the molecule due to its production method. From the viewpoint of obtaining a resin composition exhibiting good storage stability and eventually realizing an insulating layer exhibiting desired characteristics, the content of isocyanate groups in the carbodiimide compound (also referred to as “NCO content”) is as follows. It is preferably at most 5 mass%, more preferably at most 4 mass%, further preferably at most 3 mass%, still more preferably at most 2 mass%, particularly preferably at most 1 mass% or at most 0.5 mass%.

  As the carbodiimide compound, a commercially available product may be used. Commercially available carbodiimide compounds include, for example, Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Ltd., and Stabacol (registered trademark) manufactured by Rhein Chemie. P, P400, and Hykadil 510.

  In combination with (B) an active ester compound, (D) a thermoplastic resin, and a certain amount or more of (E) an inorganic filler, any of dielectric tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength From the viewpoint of obtaining an insulating layer having excellent properties, the content of the carbodiimide compound in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and 3% by mass or more, 4% by mass or more, or 5% by mass. % By mass or more is more preferable. The upper limit of the content of the carbodiimide compound is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

<(D) thermoplastic resin>
The resin composition of the present invention contains a thermoplastic resin as the component (D).

  As the thermoplastic resin, for example, a phenoxy resin, a polyvinyl acetal resin, an acid anhydride group-containing vinyl resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyamideimide resin, a styrene-based elastomer resin, a polyether sulfone resin, a polyphenylene ether resin and Polysulfone resin and the like can be mentioned. The thermoplastic resin may be used alone or in combination of two or more. The thermoplastic resin preferably has a glass transition temperature of 80 ° C. or higher.

  Among them, in combination with (B) an active ester compound, (C) a carbodiimide compound, and a certain amount or more of (E) an inorganic filler, dielectric tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength are improved. From the viewpoint of obtaining a more excellent insulating layer, the thermoplastic resin is one selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, a vinyl resin containing an acid anhydride group, a polyimide resin, a polyamideimide resin, and a styrene-based elastomer resin. It is preferable that it is above.

  From the viewpoint of obtaining an insulating layer having good mechanical strength, the weight average molecular weight of the thermoplastic resin is preferably 10,000 or more, more preferably 15,000 or more, further preferably 20,000 or more, and still more preferably 25,000 or more, or 30,000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the thermoplastic resin is preferably 200,000 or less, more preferably 180,000 or less, further preferably 160,000 or less, and still more preferably 150,000 or less. The weight average molecular weight of the thermoplastic resin can be measured, for example, by gel permeation chromatography (GPC). In detail, the weight average molecular weight (in terms of polystyrene) of the thermoplastic resin is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  In combination with (B) an active ester compound, (C) a carbodiimide compound, and a certain amount or more of (E) an inorganic filler, any of dielectric tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength From the viewpoint of obtaining an insulating layer also having excellent properties, particularly from the viewpoint of obtaining an insulating layer having a high peel strength, the thermoplastic resin contains one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms or carbon- It preferably has a functional group containing a carbon double bond. Examples of such a functional group include a hydroxyl group, a carboxy group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, a diimide group, and an alkenyl group. , An allene group and a ketene group. As the acid anhydride group, a carboxylic acid anhydride group is preferable. Preferable examples of the alkenyl group include a vinyl group, an allyl group, and a styryl group. By using a thermoplastic resin having such a functional group, the glass transition temperature of the obtained insulating layer tends to be high, and an insulating layer exhibiting good heat resistance can be realized. When the thermoplastic resin contains such a functional group, the functional group equivalent of the thermoplastic resin is preferably 100,000 or less, more preferably 90000 or less, 80000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40000 or less, 30000 or less, It is 20,000 or less, 10,000 or less, 8000 or less, 6000 or less, or 5000 or less. The lower limit of the functional group equivalent is not particularly limited, but may be usually 50 or more, 100 or more.

  Hereinafter, a preferred thermoplastic resin will be described in more detail, but according to a known procedure, a thermoplastic resin obtained by further adding the above functional group to the thermoplastic resin shown below can also be suitably used in the present invention. .

  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, adamantane skeleton, terpene Phenoxy resins having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. Specific examples of the phenoxy resin include “1256” and “4250” (both phenoloxy resins containing a bisphenol A skeleton), “YX8100” (phenoxy resin containing a bisphenol S skeleton), and “YX6954” (produced by Mitsubishi Chemical Corporation). Bisphenol acetophenone skeleton-containing phenoxy resin), as well as "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YL7553", "YL6794", "YL7213" manufactured by Mitsubishi Chemical Corporation. "YL7290" and "YL7482".

  Specific examples of the polyvinyl acetal resin include Electrified Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., Eslek BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd., KS series (for example, KS-1), BL series, BM series and the like.

  The acid anhydride group-containing vinyl resin can be obtained, for example, by copolymerizing the acid anhydride group-containing monomer (d1) and another monomer (d2). Examples of the acid anhydride group-containing monomer (d1) include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride. The other monomer (d2) is not particularly limited as long as it can be copolymerized with the acid anhydride group-containing monomer (d1), and includes ethylenically unsaturated monomers such as (meth) acrylic acid, (meth) acrylic acid ester, and styrene. May be used. Specific examples of the acid anhydride group-containing vinyl resin include “EF-30”, “EF-40”, “EF-60”, and “EF-80” manufactured by CRAY VALLEY HSC.

  Specific examples of the polyimide resin include “Ricacoat SN-20” and “Ricacoat PN-20” manufactured by Shin Nippon Rika Co., Ltd., and “Unidick V-8000” manufactured by DIC Corporation. Specific examples of the polyimide resin include linear polyimide (JP-A-2006-37083) obtained by reacting a difunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic anhydride, and a polyimide containing a polysiloxane skeleton ( Modified polyimides such as JP-A-2002-12667, JP-A-2000-319386, and WO2010 / 53186.

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

  Examples of the styrene-based elastomer resin include, for example, a block copolymer including a block of styrene or an analog thereof as at least one end block, and including an elastomer block of a conjugated diene or a hydrogenated product thereof as at least one intermediate block. Can be. Specifically, styrene-butadiene diblock copolymer, styrene-butadiene block copolymer, styrene-isoprene diblock copolymer, styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, Examples include hydrogenated styrene-isoprene diblock copolymer, hydrogenated styrene-isoprene triblock copolymer, and hydrogenated styrene-butadiene random copolymer. Specific examples of the styrene-based elastomer resin include Asaprene, Tufprene, and Asaflex manufactured by Asahi Kasei Kogyo Co., Ltd .; and Hibler and Septon manufactured by Kuraray Co., Ltd.

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

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

  In combination with (B) an active ester compound, (C) a carbodiimide compound, and a certain amount or more of (E) an inorganic filler, any of dielectric tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength In respect of obtaining an insulating layer having excellent characteristics, the content of the thermoplastic resin in the resin composition is preferably equal to or greater than 0.5% by mass, more preferably equal to or greater than 1% by mass, and still more preferably equal to or greater than 1.5% by mass. And more preferably 2% by mass or more. The upper limit of the content of the thermoplastic resin is not particularly limited, but is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and even more preferably 15% by mass or less.

<(E) Inorganic filler>
The resin composition of the present invention contains a certain amount or more of an inorganic filler as the component (E).

  In combination with (B) an active ester compound, (C) a carbodiimide compound, and (D) a thermoplastic resin, they are excellent in any of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength. From the viewpoint of obtaining an insulating layer, particularly from the viewpoint of obtaining an insulating layer having a low dielectric loss tangent and a low coefficient of thermal expansion, the content of the inorganic filler in the resin composition layer is 40% by mass or more, preferably 45% by mass or more, It is more preferably at least 50% by mass, and even more preferably at least 55% by mass or at least 60% by mass. In the present invention in which an inorganic filler is used in combination with (B) an active ester compound, (C) a carbodiimide compound, and (D) a thermoplastic resin, the elongation at break, the surface roughness, and the peel strength are reduced. In addition, the content of the inorganic filler can be further increased. For example, the content of the inorganic filler in the resin composition is 62% by mass or more, 64% by mass or more, 66% by mass or more, 68% by mass or more, 70% by mass or more, 72% by mass or more, or 74% by mass or more. May be increased to

  The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less, from the viewpoint of the mechanical strength of the obtained insulating layer. .

  Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, and the like, and silica is particularly preferred. That. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As the silica, spherical silica is preferable. One kind of the inorganic filler may be used alone, or two or more kinds may be used in combination. Examples of commercially available spherical fused silica include “SO-C2” and “SO-C1” manufactured by Admatechs.

  The average particle diameter of the inorganic filler is not particularly limited, but is preferably 3 μm or less, more preferably 2 μm or less, and more preferably 1 μm or less, 0.7 μm or less, from the viewpoint of obtaining an insulating layer on which fine wiring can be formed. 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less is more preferable. On the other hand, the average particle size of the inorganic filler is preferably 0.01 μm or more from the viewpoint of obtaining a resin varnish having an appropriate viscosity and having good handleability when forming a resin varnish using the resin composition. It is more preferably at least 0.03 μm, even more preferably at least 0.05 μm, 0.07 μm or 0.1 μm. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, it can be measured by preparing a particle size distribution of the inorganic filler on a volume basis by using a laser diffraction type particle size distribution measuring device, and setting a median diameter as an average particle size. As the measurement sample, a sample in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, "LA-500", "LA-750", "LA-950", etc. manufactured by Horiba, Ltd. can be used.

  From the viewpoint of increasing the moisture resistance and dispersibility of the inorganic filler, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, titanate-based coupling agents It is preferably treated with one or more surface treatment agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. And “SZ-31” (hexamethyldisilazane).

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

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

<(F) Curing accelerator>
The resin composition of the present invention may further contain a curing accelerator as the component (F).

  Examples of the curing accelerator include, but are not particularly limited to, amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, guanidine-based curing accelerators, and the like; amine-based curing accelerators, imidazole-based curing agents, and the like. Accelerators are preferred. The curing accelerator may be used alone or in combination of two or more.

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

  Examples of the imidazole-based curing accelerator include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-Ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline; and adducts of imidazole compounds and epoxy resins; 2-ethyl-4-methylimidazole, 1-benzyl-2- Phenylimidazole is preferred.

  Examples of the phosphorus-based curing accelerator include triphenylphosphine, a 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 preferred.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  Above all, in combination with the above components (A) to (E), from the viewpoint of obtaining an insulating layer having more excellent dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength, as a curing accelerator, 4-dimethylaminopyridine, 1-benzyl-2-phenylimidazole are particularly preferred.

  The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.005% by mass to 1% by mass, and more preferably 0.01% by mass to 0.5% by mass.

<Other ingredients>
-Curing agent-
The resin composition of the present invention may further contain a curing agent (however, excluding the component (B)). By containing the curing agent, the insulation reliability, peel strength, and mechanical strength of the obtained insulating layer can be increased. The curing agent is not particularly limited, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a benzoxazine-based curing agent. The curing agents may be used alone or in combination of two or more. Among these, in combination with the above components (A) to (E), from the viewpoint of obtaining an insulating layer having more excellent dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength, a phenolic curing agent is used. , Naphthol-based curing agents and cyanate ester-based curing agents are preferred.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of peel strength, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferred. Among them, a phenol novolak resin containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength to a conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and “MEH-7851” manufactured by Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD-2090" manufactured by DIC Corporation. And the like.

  The cyanate ester-based curing agent is not particularly limited. For example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type curing agent, dicyclopentadiene type cyanate ester type curing agent, bisphenol type (bisphenol A type, (Bisphenol F type, bisphenol S type, etc.) cyanate ester type curing agents, and prepolymers in which these are partially triazined. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), and 4,4′-ethylidene diphenyl Dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, Bifunctional cyanate resins such as 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether and bis (4-cyanatephenyl) ether, phenol novolak and cresol novolak Invite from etc. Polyfunctional cyanate resin is, these cyanate resins and partially triazine of prepolymer. Commercially available cyanate ester-based curing agents include “PT30” and “PT60” (both are phenol novolac-type polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan K.K. Is a tripolymer which is triazine-modified to form a trimer).

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

  The content of the curing agent in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 6% by mass from the viewpoint of the mechanical strength of the obtained insulating layer. .

-Flame retardant-
The resin composition of the present invention may further contain a flame retardant. Examples of the flame retardant include organic phosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone-based flame retardants, metal hydroxides, and the like. The flame retardants may be used alone or in a combination of two or more. The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 9% by mass.

-Organic filler-
The resin composition of the present invention may further contain an organic filler. As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

  The rubber particles are not particularly limited as long as the resin particles exhibiting rubber elasticity are subjected to a chemical crosslinking treatment, and are fine particles of a resin insoluble and infusible in an organic solvent, for example, acrylonitrile butadiene rubber particles, butadiene rubber particles, And acrylic rubber particles. Specific examples of the rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, and IM101 (all manufactured by Aika Kogyo) paraloid EXL2655. And EXL2602 (all manufactured by Kureha Chemical Industry Co., Ltd.).

  The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the organic filler is measured using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by making a standard and making the median diameter the average particle diameter. The content of the organic filler in the resin composition is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 5% by mass.

  The resin composition of the present invention may further contain other components as necessary. Such other components include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, and thickeners, defoamers, leveling agents, adhesion-imparting agents, coloring agents and curable resins. And the like.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the components are added with a solvent or the like as necessary, and mixed and dispersed using a rotary mixer or the like.

  The resin composition of the present invention can provide a cured product (insulating layer) having a low dielectric loss tangent. The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of dielectric loss tangent>. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonator perturbation method. From the viewpoint of preventing heat generation at high frequencies, reducing signal delay and signal noise, the dielectric loss tangent is preferably equal to or less than 0.010, more preferably equal to or less than 0.009, and equal to or less than 0.008, 0.007 or 0.006. More preferred. Although the lower limit of the dielectric loss tangent is preferably as low as possible, it can usually be 0.001 or more.

  The resin composition of the present invention can provide a cured product (insulating layer) having a low coefficient of thermal expansion. The coefficient of linear thermal expansion of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of glass transition temperature and coefficient of linear thermal expansion>. Specifically, the average linear thermal expansion coefficient in the plane direction at 25 to 150 ° C. can be measured by performing a thermomechanical analysis by a tensile load method. The cured product of the resin composition of the present invention is preferably at most 40 ppm / ° C, more preferably at most 35 ppm / ° C, still more preferably at most 30 ppm / ° C, even more preferably at most 25 ppm / ° C, particularly preferably at most 20 ppm / ° C. Can be shown. Although the lower limit of the linear thermal expansion coefficient is not particularly limited, it is usually 1 ppm / ° C. or more.

  The resin composition of the present invention can provide a cured product (insulating layer) showing good elongation at break. The elongation at break of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of elongation at break>. Specifically, it can be measured by a tensile test method in accordance with Japanese Industrial Standards (JIS K7127). The cured product of the resin composition of the present invention is preferably at least 2%, more preferably at least 2.1%, further preferably at least 2.2%, still more preferably at least 2.3%, at least 2.4%. Or an elongation at break of 2.5% or more. The upper limit of the elongation at break is preferably 30% or less, more preferably 20% or less, and further preferably 10% or less.

  The resin composition of the present invention can provide a cured product (insulating layer) having low surface roughness. The arithmetic average roughness (Ra) of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of arithmetic average roughness (Ra)>. It is desired that the surface of the insulating layer after the roughening treatment has small surface irregularities from the viewpoint of reducing loss of an electric signal. Specifically, the arithmetic average roughness (Ra) of the insulating layer surface after curing the resin composition to form an insulating layer and roughening the surface of the insulating layer is preferably 140 nm or less, and 130 nm or less. The following is more preferable, 120 nm or less is still more preferable, 110 nm or less is still more preferable, and 100 nm or less is especially preferable. From the viewpoint of obtaining a sufficient peel strength, the lower limit of the arithmetic average roughness (Ra) is preferably 5 nm or more, more preferably 10 nm or more, and still more preferably 15 nm or more.

  The resin composition of the present invention can provide a cured product (insulating layer) having high peel strength. The peel strength of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of peel strength of plated conductor layer>. Specifically, when the resin composition is cured to form an insulating layer, and the surface of the insulating layer after the roughening treatment is plated to form a conductive layer, the peel between the obtained conductive layer and the insulating layer is peeled off. The strength is preferably at least 0.50 kgf / cm, more preferably at least 0.55 kgf / cm, even more preferably at least 0.60 kgf / cm. The upper limit of the peel strength is not particularly limited, but may be usually 1.2 kgf / cm or less.

  The resin composition of the present invention can also provide a cured product (insulating layer) having a high glass transition temperature (Tg). The glass transition temperature (Tg) of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of elongation at break>. The cured product of the resin composition of the present invention can exhibit a glass transition temperature (Tg) of preferably 165 ° C or higher, more preferably 170 ° C or higher, 175 ° C or higher, or 180 ° C or higher. The upper limit of the glass transition temperature (Tg) is not particularly limited, but is usually 250 ° C. or lower.

  The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board). Can be more suitably used as a resin composition for forming a conductive layer (resin composition for an interlayer insulating layer of a printed wiring board), on which a conductive layer is formed by plating to form an interlayer insulating layer. It can be more suitably used as a resin composition (a resin composition for an interlayer insulating layer of a printed wiring board in which a conductor layer is formed by plating). The resin composition of the present invention also requires a resin composition, such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a filling resin, and a component filling resin. It can be used in a wide range of applications.

[Adhesive film]
Although the resin composition of the present invention can be used in a varnish state, it is generally preferable to use it in the form of an adhesive film industrially.

  The adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is formed from the resin composition of the present invention.

  The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less, still more preferably 50 μm or less or 40 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 is usually 5 μm or more or 10 μm or more.

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

  When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) or polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). .), Acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), and polyethers. Ketone, polyimide and the like can be mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a 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. May be used.

  The support may have been subjected to a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used in the release layer of the support having a release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Commercially available release agents include, for example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Co., Ltd., which are alkyd resin release agents.

  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 the support is a support with a release layer, the thickness of the entire support with a release layer is preferably within the above range.

  The adhesive film is prepared, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. It can be manufactured by the following.

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

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

  In the adhesive film, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface on the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and to prevent scratches. The adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

  The adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). And a resin composition for forming an interlayer insulating layer on which a conductive layer is formed by plating (an interlayer of a printed wiring board on which a conductive layer is formed by plating). (For an insulating layer).

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.

In one embodiment, the printed wiring board of the present invention can be manufactured by a method including the following steps (I) and (II) using the above-mentioned adhesive film.
(I) Step of laminating an adhesive film on an inner layer substrate such that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) Step of thermosetting the resin composition layer to form an insulating layer

  The “inner layer substrate” used in the step (I) mainly means a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when manufacturing a printed wiring board, an inner circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the “inner layer board” in the present invention.

  The lamination of the inner layer substrate and the adhesive film can be performed, for example, by heat-pressing the adhesive film to the inner layer substrate from the support side. Examples of a member (hereinafter, also referred to as a “thermocompression member”) for thermocompression bonding the adhesive film to the inner layer substrate include a heated metal plate (SUS mirror plate or the like) or a metal roll (SUS roll). It is preferable that the thermocompression bonding member is not pressed directly on the adhesive film, but is pressed via an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner substrate.

  The lamination of the inner substrate and the adhesive film may be performed by a vacuum lamination method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0 ° C. .29 MPa to 1.47 MPa, and the heat-compression bonding time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure condition of a pressure of 26.7 hPa or less.

  Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., and a vacuum applicator manufactured by Nichigo Morton Co., Ltd.

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

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

  In the step (II), the insulating layer is formed by thermosetting the resin composition layer.

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

  For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 210 ° C, more preferably 170 ° C to 170 ° C). The curing time can be in a range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

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

  In manufacturing the printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer on the surface of the insulating layer may be further performed. Good. These steps (III) to (V) may be performed according to various methods used for manufacturing a printed wiring board and known to those skilled in the art. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or It may be performed between IV) and step (V).

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

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions usually used when forming an insulating layer of a printed wiring board can be adopted. For example, a swelling process using a swelling solution, a roughening process using an oxidizing agent, and a neutralizing process using a neutralizing solution can be performed in this order to roughen the insulating layer. The swelling solution is not particularly limited, but includes an alkali solution, a surfactant solution, and the like, and is preferably an alkali solution. As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan KK. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 ° C to 90 ° C for 1 minute to 20 minutes. Although it does not specifically limit as an oxidizing agent, For example, alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in aqueous solution of sodium hydroxide is mentioned. The roughening treatment using 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 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganate solution is preferably from 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate CP and Dosing Solution Securigans P manufactured by Atotech Japan KK. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercial product, for example, Reduction Solution Securiganto P manufactured by Atotech Japan Co., Ltd. is exemplified. The treatment with the neutralizing solution can be performed by immersing the roughened surface with the oxidizing agent solution in the neutralizing solution at 30 ° C. to 80 ° C. for 5 minutes to 30 minutes.

  Step (V) is a step of forming a conductor layer on the surface of the insulating layer.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductive layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper Nickel alloy and copper-titanium alloy). Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper A nickel alloy or an alloy layer of copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable. Metal layers are more preferred.

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

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

  The conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. Hereinafter, an example in which a conductor layer is formed by a semi-additive method will be described.

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

  As described above, by manufacturing a printed wiring board using the resin composition of the present invention, an insulating layer having excellent properties such as dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength Can be advantageously manufactured.

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board of the present invention. Examples of the semiconductor device include various semiconductor devices used for electric appliances (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

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

  The method of mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, and no bump A mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like can be given. Here, the “mounting method using the bump-less build-up layer (BBUL)” refers to a “mounting method for directly embedding a semiconductor chip in a recess of a printed wiring board and connecting the semiconductor chip to wiring on the printed wiring board”. It is.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. “Parts” means parts by mass.

[Measurement method and evaluation method]
First, various measurement methods and evaluation methods will be described.

<Preparation of sample for measuring peel strength and arithmetic average roughness (Ra value)>
(1) Underlayer treatment of inner layer circuit board Glass cloth base epoxy resin double-sided copper-clad laminate on which inner layer circuit is formed (copper foil thickness: 18 μm, board thickness: 0.4 mm, “R1515A” manufactured by Panasonic Corporation) Both surfaces were etched at 1 μm using “CZ8101” manufactured by Mec Corporation to roughen the copper surface.

(2) Lamination of Adhesive Film The adhesive film produced in each of Examples and Comparative Examples was subjected to a batch-type vacuum press laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.) to form a resin composition layer having an inner layer circuit. Laminating treatment was performed on both sides of the inner circuit board so as to be bonded to the board. The lamination treatment was performed by reducing the pressure to 13 hPa or less by reducing the pressure for 30 seconds, and then performing pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition After laminating the adhesive film, the resin composition layer was thermally cured at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to form an insulating layer. Thereafter, the support was peeled off to expose the insulating layer.

(4) Roughening treatment The inner layer circuit board with the exposed insulating layer was immersed in a swelling solution (“Swelling Dip Securiganto P”, manufactured by Atotech Japan KK, aqueous sodium hydroxide solution containing diethylene glycol monobutyl ether) at 60 ° C. for 10 minutes. Immersion, then immersion in an oxidizing agent ("Concentrate Compact CP" manufactured by Atotech Japan KK, aqueous solution of potassium permanganate concentration of about 6% by mass and sodium hydroxide concentration of about 4% by mass) at 80 ° C for 20 minutes. Finally, it was immersed in a neutralizing solution (“Reduction Solution Securiganto P”, manufactured by Atotech Japan KK, aqueous hydroxylamine sulfate solution) at 40 ° C. for 5 minutes. Then, it dried at 80 degreeC for 30 minutes. The obtained substrate is referred to as “evaluation substrate a”.

(5) Formation of Conductive Layer A conductive layer was formed on the roughened surface of the insulating layer according to the semi-additive method.
That is, the substrate after the roughening treatment was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Next, after annealing at 150 ° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm, and annealing was performed at 200 ° C. for 60 minutes. The obtained substrate is referred to as “evaluation substrate b”.

<Measurement of arithmetic average roughness (Ra)>
For the evaluation substrate a, the Ra value was determined by using a non-contact type surface roughness meter (“WYKO NT3300” manufactured by Becoinstruments Co., Ltd.) using a VSI contact mode and a 50 × lens with a measurement range of 121 μm × 92 μm. . It was determined by determining the average of 10 randomly selected points.

<Measurement of peel strength of plated conductor layer>
The measurement of the peel strength of the insulating layer and the conductor layer was performed on the evaluation substrate b in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a cut of 10 mm in width and 100 mm in length is made in the conductor layer of the evaluation board b, and one end thereof is peeled off and gripped with a gripper, and at room temperature in the vertical direction at a speed of 50 mm / min. The load (kgf / cm) when 35 mm was peeled off was measured to determine the peel strength. A tensile tester (“AC-50C-SL” manufactured by TSE) was used for the measurement.

<Measurement of elongation at break>
The adhesive films produced in Examples and Comparative Examples were heated at 200 ° C. for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as “evaluated cured product c”. The cured product c for evaluation was subjected to a tensile test using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) in accordance with Japanese Industrial Standards (JIS K7127) to measure the elongation at break.

<Measurement of glass transition temperature and coefficient of linear thermal expansion>
The cured product c for evaluation is cut into a test piece having a width of about 5 mm and a length of about 15 mm, and a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation) is used to obtain a thermomechanical product by a tensile load method. Analysis was carried out. Specifically, after the test piece was mounted on the thermomechanical analyzer, the measurement was continuously performed twice at a load of 1 g and at a heating rate of 5 ° C./min. In the second measurement, the glass transition temperature (Tg; ° C) and the average coefficient of linear thermal expansion (CTE; ppm / ° C) in the range from 25 ° C to 150 ° C were calculated.

<Measurement of dielectric loss tangent>
The cured product c for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. The dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. The measurement was performed on two test pieces, and the average value was calculated.

<Example 1>
Bisphenol A type epoxy resin ("828US", Mitsubishi Chemical Corporation, epoxy equivalent about 180) 10 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent about 269) 25 parts, bixylenol 25 parts of epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 185) and phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation), 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass. 20) was heated and dissolved in 30 parts of solvent naphtha while stirring. After cooling to room temperature, 15 parts of a triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, a hydroxyl equivalent of about 151, a 2-methoxypropanol solution having a solid content of 50%) were added thereto. 20 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, an active group equivalent of about 223, a toluene solution of a nonvolatile component of 65% by mass), and a carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Inc.) 20 parts of an NCO content of 0% by mass, a non-volatile component of 50% by mass in a toluene solution) 20 parts, a curing accelerator (4-dimethylaminopyridine (DMAP), a solid content of 10% by mass in an MEK solution) 3 parts, and an aminosilane-based coupling agent ( Spherical silica (average particle size 0.5 μm, surface-treated with Shin-Etsu Chemical Co., Ltd. “KBM573”, Admatechs “SO C2 ") 275 parts were mixed, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

  As a support, a PET film with an alkyd resin-based release layer (“AL5” manufactured by Lintec Co., Ltd., thickness 38 μm) was prepared. A resin varnish is uniformly applied on the release layer of the support so that the thickness of the resin composition layer after drying is 30 μm, and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 4 minutes. Then, an adhesive film was produced.

<Example 2>
A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that the amount of the carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Inc., a toluene solution having a nonvolatile content of 50% by mass) was changed to 80 parts. did.

<Example 3>
100 parts by weight of spherical silica (average particle size: 0.5 μm, Admatex “SO-C2”) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the composition was changed to.

<Example 4>
275 parts of spherical silica (average particle diameter: 0.5 μm, Admatex “SO-C2”) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Except that 275 parts of spherical silica (average particle diameter: 0.3 μm, Admatex “SO-C1”) surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was used. In the same manner as in Example 1, a resin varnish and an adhesive film were produced.

<Example 5>
An active ester compound (“EXB9050L-62M” manufactured by DIC Corporation) was mixed with 20 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution of an active group equivalent of about 223 and a nonvolatile component of 65% by mass). Resin varnish and adhesive film were prepared in the same manner as in Example 1 except that the amount of the active group was changed to 21 parts (MEK solution containing an active group equivalent of about 334 and a nonvolatile component of 62% by mass).

<Example 6>
3 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution having a solid content of 10% by mass) was added to a curing accelerator (“1B2PZ” manufactured by Shikoku Chemicals Co., Ltd., 1-benzyl-2-phenylimidazole, A resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the amount was changed to 6 parts by weight (MEK solution of 10% by mass).

<Example 7>
20 parts of a carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution of 50% by mass of a non-volatile component) was mixed with 20 parts of a carbodiimide compound (“V-07” manufactured by Nisshinbo Chemical Inc., NCO content 0.5 mass). %, A toluene solution containing 50% by mass of a nonvolatile component), and a resin varnish and an adhesive film were prepared in the same manner as in Example 1.

<Example 8>
20 parts of a phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK having a solid content of 30% by mass and cyclohexanone) was mixed with a polyvinyl butyral resin (glass transition temperature 105 ° C., manufactured by Sekisui Chemical Co., Ltd.) KS-1 ", a resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the amount was changed to 40 parts (a 1: 1 solution of ethanol and toluene containing 15% by mass of a nonvolatile component).

<Example 9>
20 parts of a phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK having a solid content of 30% by mass and cyclohexanone) was mixed with an acid anhydride group-containing vinyl resin (“EF-30” manufactured by CRAY VALLEY HSC). A resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the amount was changed to 12 parts (cyclohexanone solution having a solid content of 50%).

<Example 10>
20 parts of a phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass) were mixed with a polyimide resin (“SN-20” manufactured by Nippon Rika Co., Ltd.) A resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the amount was changed to 30 parts of a 20% N-methyl-2-pyrrolidone (NMP) solution).

<Example 11>
20 parts of a phenoxy resin (“YL7553BH30”, manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass) were mixed with a polyimide resin (“Unidick V-8000”, manufactured by DIC Corporation), a nonvolatile component. A resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the amount was changed to 15 parts of a 40% by mass ethyl diglycol acetate solution.

<Example 12>
10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 180) was changed to 10 parts of an alicyclic epoxy resin having an ester skeleton ("CELLOXIDE 2021P" manufactured by Daicel Corporation). Except for the above, a resin varnish and an adhesive film were produced in the same manner as in Example 2.

<Example 13>
The blending amount of the triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, a hydroxyl group equivalent of about 151, a 2-methoxypropanol solution having a solid content of 50%) was changed to 5 parts, and the benzoxazine-based A resin varnish and an adhesive film were produced in the same manner as in Example 2, except that 10 parts of a curing agent ("P-d" manufactured by Shikoku Chemicals Co., Ltd., cyclohexanone solution having a solid content of 50%) was added.

<Example 14>
9. 20 parts of a phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK having a solid content of 30% by mass and cyclohexanone) was mixed with the siloxane skeleton-containing polyimide resin of Synthesis Example 1 (solid content: 55% by mass). A resin varnish and an adhesive film were produced in the same manner as in Example 2 except that the amount was changed to 9 parts.

[Synthesis Example 1]
20 parts of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) was placed in a 500 mL separable flask equipped with a water metering receiver connected to a reflux condenser, a nitrogen inlet tube and a stirrer, 70.9 parts of γ-butyrolactone, 7 parts of toluene, 61.5 parts of diaminosiloxane (“X-22-9409” manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 665), 2,6-bis (1-hydroxy-1) -Trifluoromethyl-2,2,2-trifluoroethyl) -1,5-naphthalenediamine (HFA-NAP) (7.4 parts) was added, and the mixture was stirred at 45 ° C. for 2 hours under a nitrogen stream to carry out a reaction. Was. Then, the reaction solution was heated and condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. When it was confirmed that a predetermined amount of water had accumulated in the water content receiver and no outflow of water was observed, the temperature was further increased and the mixture was stirred at 200 ° C. for 1 hour. Thereafter, the system was cooled to complete the process, and a varnish containing 55% by mass of a siloxane skeleton-containing polyimide resin having a hexafluoroisopropanol group (HFA group) was produced. In this case, the content of the siloxane structure in the resin was 70.9% by mass, and the HFA group equivalent was 2,881 g / mol.

<Example 15>
10 parts bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828US", epoxy equivalent about 180) 10 parts bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent about 235) 10 parts A resin varnish and an adhesive film were prepared in the same manner as in Example 1 except for performing the above.

<Comparative Example 1>
A resin varnish and an adhesive film were produced in the same manner as in Example 1, except that 20 parts of a carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Inc., a toluene solution of 50% by mass of a nonvolatile component) was not used.

<Comparative Example 2>
A resin was prepared in the same manner as in Example 1, except that 20 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, an active group equivalent of about 223, a toluene solution of a nonvolatile component of 65% by mass) was not used. A varnish and an adhesive film were produced.

<Comparative Example 3>
Resin varnish and adhesive film in the same manner as in Example 1 except that 20 parts of a phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK having a solid content of 30% by mass and cyclohexanone) was not used. Was prepared.

<Comparative Example 4>
The amount of spherical silica (average particle size: 0.5 μm, “SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) is adjusted to 40. A resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the parts were changed to parts.

  Table 1 shows the results.

Claims (18)

  It contains (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin, and (E) an inorganic filler, and the content of the (E) component is non-volatile in the resin composition. A resin composition, which has a content of 40% by mass or more when the component is 100% by mass.   The resin composition according to claim 1, wherein the component (D) has a weight average molecular weight of 10,000 to 200,000.   The component (D) is a thermoplastic resin having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom or a functional group containing a carbon-carbon double bond. 3. The resin composition according to 2.   (D) Component is a hydroxyl group, a carboxy group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, a diimide group, an alkenyl group, The resin composition according to any one of claims 1 to 3, which is a thermoplastic resin having at least one functional group selected from the group consisting of an allene group and a ketene group.   The component (D) is at least one thermoplastic resin selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, a vinyl resin containing an acid anhydride group, a polyimide resin, a polyamideimide resin, and a styrene-based elastomer resin. Item 5. The resin composition according to any one of Items 1 to 4.   The resin composition according to any one of claims 1 to 5, wherein the component (C) has a weight average molecular weight of 500 to 5,000.   The resin composition according to any one of claims 1 to 6, wherein the NCO content of the component (C) is 5% by mass or less.   The resin composition according to any one of claims 1 to 7, wherein the content of the component (E) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to any one of claims 1 to 8, wherein the component (E) has an average particle diameter of 0.01 µm to 3 µm.   The resin composition according to any one of claims 1 to 9, wherein the component (E) is silica.   The resin composition according to any one of claims 1 to 10, further comprising (F) a curing accelerator.   The resin composition according to claim 11, wherein the component (F) is 4-dimethylaminopyridine or 1-benzyl-2-phenylimidazole.   The arithmetic average roughness (Ra) after hardening a resin composition to form an insulating layer and subjecting the surface of the insulating layer to a roughening treatment is 140 nm or less, according to any one of claims 1 to 12. Resin composition.   The resin composition according to any one of claims 1 to 13, wherein the cured product of the resin composition has an elongation at break of 2% or more.   The resin composition according to any one of claims 1 to 14, wherein a cured product of the resin composition has a glass transition temperature (Tg) of 165 ° C or higher.   An adhesive film comprising: a support; and a layer of the resin composition according to claim 1 bonded to the support.   A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 1.   A semiconductor device comprising the printed wiring board according to claim 17.