JP2021119245A - Resin composition, adhesive film, printed wiring board and semiconductor device - Google Patents

Abstract

To provide a resin composition which is used in the manufacture of a printed wiring board and can provide an insulating layer excellent in all the properties of dielectric loss tangent, thermal expansion coefficient, elongation at break, surface roughness and peel strength.SOLUTION: A resin composition comprises an epoxy resin (A), an active ester compound (B), a carbodiimide compound (C), a thermoplastic resin (D) and an inorganic filler (E). If the non-volatile component of the resin composition is taken as 100 mass%, the content of inorganic filler (E) is 40 mass% or more.SELECTED DRAWING: None

Description

The present invention relates to resin compositions. 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 for printed wiring boards, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing the resin composition. For example, Patent Document 1 discloses a technique of curing a resin composition containing an epoxy resin, an active ester compound and a carbodiimide compound to form an insulating layer having a low dielectric loss tangent.

Due to the tendency of lightness, thinness, shortness and smallness in recent years, the number of laminated printed wiring boards tends to increase due to build-up, but as the number of laminated layers increases, cracks and circuit distortion occur due to the difference in thermal expansion between the insulating layer and the conductor layer. Is a problem. As a technique for suppressing such problems of cracks and circuit distortion, for example, Patent Document 2 states that the coefficient of thermal expansion of the formed insulating layer is suppressed by increasing the content of the inorganic filler in the resin composition. The technology is disclosed.

Japanese Unexamined Patent Publication No. 2006-335834 Japanese Unexamined Patent Publication No. 2010-202865

In the production of a printed wiring board, the present inventors have stated that the resin composition described in Patent Document 1 is blended with an inorganic filler at a high content in order to form an insulating layer having a low dielectric loss tangent and a low thermal expansion rate. I tried. While the obtained resin composition provides an insulating layer exhibiting the desired dielectric loss tangent and coefficient of thermal expansion, it may result in an insulating layer having inferior characteristics such as elongation at break, surface roughness, and peel strength. The present inventors have found.

The present invention provides a resin composition capable of providing an insulating layer having excellent properties of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength in the production of a printed wiring board. Is the subject.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by the following specific resin composition, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) epoxy resin, (B) active ester compound, (C) carbodiimide compound, (D) thermoplastic resin and (E) inorganic filler, and the content of (E) component is A resin composition containing 40% by mass or more when the non-volatile component in the resin is 100% by mass.
[2] The resin composition according to [1], wherein the weight average molecular weight of the component (D) is 1000 to 20000.
[3] The component (D) is a thermoplastic resin having one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms, or a functional group containing 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 one or more thermoplastic resins selected from the group consisting of phenoxy resins, polyvinyl acetal resins, acid anhydride group-containing vinyl resins, polyimide resins, polyamideimide resins and styrene-based elastomer resins. 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 weight average molecular weight of the component (C) is 500 to 5000.
[7] The resin composition according to any one of [1] to [6], wherein the NCO content of the component (C) is 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 non-volatile component in the resin composition is 100% by mass. ..
[9] The resin composition according to any one of [1] to [8], wherein the average particle size of the component (E) is 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 arithmetic average roughness (Ra) after curing the resin composition to form an insulating layer and roughening the surface of the insulating layer is 140 nm or less. The resin composition described in Crab.
[14] The resin composition according to any one of [1] to [13], wherein the cured product of the resin composition has a breaking point elongation 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 of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength in the production of a printed wiring board. can do.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof.

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

When (E) an inorganic filler is blended in a resin composition containing (A) epoxy resin, (B) active ester compound and (C) carbodiimide compound at a high content, the obtained resin composition has low dielectric constant. The present inventors have found that while providing an insulating layer exhibiting a normal contact and a low thermal expansion rate, the present invention may result in an insulating layer having inferior characteristics such as breaking point elongation, surface roughness, and peel strength. By further containing (D) a thermoplastic resin, the resin composition of the present invention provides an insulating layer having excellent breaking point elongation, surface roughness and peel strength while maintaining low dielectric loss tangent and low thermal expansion coefficient. It makes it possible. In this respect, even if (D) the thermoplastic resin is added to the resin composition containing (B) the active ester compound, the desired elongation at break, surface roughness and peel strength are not achieved. Further, even if (D) a thermoplastic resin is added to the resin composition containing (C) a carbodiimide compound, the desired elongation at break, surface roughness and peel strength are not achieved. When the (D) thermoplastic resin is added to the resin composition having a low content of the inorganic filler (E), the desired dielectric loss tangent and the coefficient of thermal expansion are not achieved in the first place. These are clearly understood from the results of the comparative examples shown later. As described above, the effects of the resin composition of the present invention include (A) epoxy resin, (B) active ester compound, (C) carbodiimide compound, (D) thermoplastic resin, and a certain amount or more ( E) This is an effect that is specifically and synergistically brought about 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).

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, and naphthol novolac type epoxy resin. Phenol novolac type epoxy resin, alicyclic epoxy resin having an 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, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy Examples thereof include resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. The epoxy resin may be used alone or in combination of two or more.

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

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, and alicyclic epoxy resin having an ester skeleton. , And an epoxy resin having a butadiene structure is preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, an alicyclic epoxy resin having an ester skeleton, and a naphthalene type epoxy resin are more preferable. The type epoxy resin and the bisphenol AF type epoxy resin are more preferable, and the bisphenol AF type epoxy resin is particularly preferable from the viewpoint of excellent balance of physical properties of the cured product. Specific examples of the liquid epoxy resin include "HP4032", "HP4032H", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), manufactured by Nippon Steel & Sumitomo Metal Corporation "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, "Selokiside 2021P" manufactured by Daicel Co., Ltd. "(Alicyclic epoxy resin having an ester skeleton) and" PB-3600 "(epoxy resin having a butadiene structure). These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin. Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. 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 "Kresornovolak type epoxy resin" manufactured by DIC Co., Ltd. N-695 "(cresol novolac type epoxy resin)," HP-7200 "(dicyclopentadiene type epoxy resin)," EXA7311 "," EXA7311-G3 "," EXA7311-G4 "," EXA7311-G4S "," HP6000 (Naftylene ether type epoxy resin), "EPPN-502H" (Trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation, "ESN485" (naphthol novolac type epoxy resin), manufactured by Mitsubishi Chemical Co., Ltd. "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin (biphenyl type epoxy resin)), "YX8800" (anthracene type epoxy resin), "YX8800" (anthracen type epoxy resin), "YX8800" "PG-100", "CG-500", "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1031S" "(Tetraphenyl ethane type epoxy resin) and the like.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 8 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) appropriate adhesiveness is provided when used in the form of an adhesive film, and ii) when used in the form of an adhesive film. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative 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 in terms of mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 6 is even 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 non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.
The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(B) 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 combined with (C) carbodiimide compound, (D) thermoplastic resin, and (E) inorganic filler described later in a certain amount or more. By using it, it is possible to provide an insulating layer having excellent properties such as dielectric positive contact, thermal expansion rate, break point elongation, surface roughness and peel strength.

As the active ester compound, a compound having two or more active ester groups in one molecule is preferable, and for example, reactions of phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds and 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 between a carboxylic acid compound and / or a thiocarboxylic acid compound and 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 used. An aromatic compound having two or more active ester groups in one molecule, which is obtained by reacting the above, is more preferable, and has a carboxylic acid compound having at least two or more carboxy groups in one molecule and a phenolic hydroxyl group. It is an aromatic compound obtained by reacting with an aromatic compound, and an aromatic compound having two or more active ester groups in one molecule is even more preferable. 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, the compatibility with the resin composition can be increased, and if the compound has an aromatic ring, it can be improved. Heat resistance can be increased.

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

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

Examples of the phenol compound include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, still more preferably 6 to 22), and preferred specific examples include hydroquinone. Resolcin, 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, fluoroglucin, benzenetriol, dicyclopentadiene type diphenol and the like. As the phenol compound, phenol novolac or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP2013-40270 may be used.

Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and preferred specific examples thereof include α-naphthol, β-naphthol, and 1 , 5-Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. As the naphthol compound, naphthol novolak may also 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, fluoroglucin, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, phosphorus atom-containing oligomer having a phenolic hydroxyl group is preferable, and catechol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, phosphorus with phenolic hydroxyl group Atomic-containing oligomers are more preferred, with 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenols, phenol novolac, and phenols. A phosphorus atom-containing oligomer having a sex hydroxyl group is more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, phenol novolac, and a phosphorus atom having a phenolic hydroxyl group. The containing oligomer is even more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, and phosphorus atom-containing oligomer having a phenolic hydroxyl group are particularly preferable. Pentadien type diphenol is particularly preferable.

The thiol compound is not particularly limited, and examples thereof include benzenedithiol and triazinedithiol.

Preferable 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 novolac, and a benzoyl product of phenol novolac. Examples thereof include 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, and among them, an active ester compound containing a dicyclopentadiene type diphenol structure and a naphthalene structure. 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.

More specifically, the compound of the following formula (1) can be mentioned as an active ester compound containing a dicyclopentadiene type diphenol structure.

（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 lowering 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, the active ester compound disclosed in JP-A-2004-277460 and 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 EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Co., Ltd.), and active ester compounds containing a dicyclopentadiene-type diphenol structure. EXB9416-70BK (manufactured by DIC Co., Ltd.) as an ester compound, DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and YLH1026 (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac. EXB9050L-62M (DIC Co., Ltd.) can be mentioned as a phosphorus atom-containing active ester compound (manufactured by DIC Co., Ltd.).

In combination with (C) carbodiimide compound, (D) thermoplastic resin, and (E) inorganic filler, which will be described later, the dielectric positive contact, thermal expansion rate, breaking point elongation, surface roughness and peel strength From the viewpoint of obtaining an insulating layer having excellent all properties, particularly from the viewpoint of obtaining an insulating layer having low surface roughness and exhibiting high peel strength, the content of the active ester compound in the resin composition is preferably 1% by mass or more. 3, 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, still more preferably 15% by mass or less.

Further, when the number of epoxy groups of the (A) epoxy resin is 1, the number of reaction groups of the (B) active ester compound is preferably 0.2 to 2, preferably 0.3, from the viewpoint of obtaining an insulating layer having good mechanical strength. ~ 1.5 is more preferable, and 0.35 to 1 is even more preferable. Here, the "number of epoxy groups of the epoxy resin" is a value obtained by dividing the solid content mass of each epoxy resin present in the resin composition by the epoxy equivalent and the total value for all the epoxy resins. Further, the "reactive group" means a functional group capable of reacting with an epoxy group, and the "number of reactive groups of the active ester compound" refers to the solid content mass of the active ester compound present in the resin composition. It is the sum of all the values divided by the reaction 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 is the above-mentioned (B) active ester compound, the later-described (D) thermoplastic resin, and a certain amount or more. When used in combination with the inorganic filler (E), it is possible to provide an insulating layer having excellent properties of dielectric positive contact, thermal expansion rate, break point elongation, surface roughness and peel strength. As the carbodiimide compound, a compound having two or more carbodiimide groups in one molecule is preferable. The carbodiimide compound may be used alone or in 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. If more than one X is present, they may have. It may be the same or different. * Indicates 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 even 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 even 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 the aromatic ring from an aromatic hydrocarbon. The arylene group preferably has 6 to 24 carbon atoms, more preferably 6 to 18, still more preferably 6 to 14, and even 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) active ester compound, (D) thermoplastic resin, and (E) inorganic filler of a certain amount or more, the dielectric positive contact, thermal expansion rate, breaking point elongation, 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. The substituent is not particularly limited, and examples thereof include 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 the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group and alkoxy group used as the substituent may be linear or branched, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 1. 6, 1 to 4, or 1 to 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 even more preferably 3 to 6. The aryl group used as the substituent is a group obtained by removing one hydrogen atom on the aromatic ring from the aromatic hydrocarbon, and the number of carbon atoms thereof is preferably 6 to 24, more preferably 6 to 18, still more preferable. Is 6 to 14, and even more preferably 6 to 10. The aryloxy group used as a substituent preferably has 6 to 24 carbon atoms, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. The acyl group used as a substituent refers to a group represented by the formula: -C (= O) -R ¹ (in the formula, R ¹ represents an alkyl group or an aryl group). The ^{alkyl group represented by R 1} may be linear or branched, and the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6. 1 to 4 or 1 to 3. The ^{number of carbon atoms of the aryl group represented by R 1} is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. The acyloxy group used as a substituent refers to a group represented by the formula: -OC (= O) -R ¹ (in the formula, R ¹ has the same meaning as described above). 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 equation (2), p represents an integer of 1-5. In combination with (B) active ester compound, (D) thermoplastic resin, and a certain amount or more of (E) inorganic filler, the dielectric loss 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 even more preferably 2 or 3.

When a plurality of X's exist in the formula (2), they may be the same or different from each other. In one 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, still more preferably 70% by mass or more, and further, when the total mass of the carbodiimide compound is 100% by mass. More preferably, it contains the structural unit represented by the formula (2) in an amount of 80% by mass or more or 90% by mass or more. The carbodiimide compound may substantially consist of the structural unit represented by the formula (2) except for the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group, which 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 that the group represented by X may have. Further, the substituent which the group used as the terminal structure may have may be the same as the substituent which 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, still more preferably 800 or more. Particularly preferably, it is 900 or more or 1000 or more. 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. Is. The weight average molecular weight of the carbodiimide compound can be measured by, for example, a gel permeation chromatography (GPC) method (in terms of polystyrene).

The carbodiimide compound may contain an isocyanate group (-N = C = O) in the molecule due to its production method. The content of isocyanate groups (also referred to as "NCO content") in the carbodiimide compound is determined from the viewpoint of obtaining a resin composition exhibiting good storage stability and, by extension, realizing an insulating layer exhibiting desired characteristics. It is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less or 0.5% by mass or less.

As the carbodiimide compound, a commercially available product may be used. Examples of commercially available carbodiimide compounds include Carbodilite (registered trademark) V-02B, V-03, V-03K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Ltd., and Stavaxol (registered trademark) manufactured by Rheinchemy Co., Ltd. Examples thereof include P, P400, and Hykazil 510.

In combination with (B) active ester compound, (D) thermoplastic resin, and a certain amount or more of (E) inorganic filler, any of dielectric positive contact, thermal expansion rate, breaking point elongation, surface roughness and peel strength 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 from the viewpoint of obtaining an insulating layer having excellent properties. More preferably by mass% or more. 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, still 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).

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, acid anhydride group-containing vinyl resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, styrene-based elastomer resin, polyethersulfone resin, polyphenylene ether resin, and the like. Examples include polysulfone resin. 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) active elastomer compound, (C) thermoplastic compound, and (E) inorganic filler of a certain amount or more, dielectric direct contact, thermal expansion rate, breaking point elongation, surface roughness and peel strength are obtained. From the viewpoint of obtaining a more excellent insulating layer, the thermoplastic resin is one selected from the group consisting of phenoxy resin, polyvinyl acetal resin, acid anhydride group-containing vinyl resin, polyimide resin, polyamideimide resin, and styrene elastomer resin. The above is preferable.

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, still more preferably 20,000 or more, 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, still more preferably 1600,000 or less, still more preferably 150,000 or less. The weight average molecular weight of the thermoplastic resin can be measured by, for example, a gel permeation chromatography (GPC) method. Specifically, 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- by Showa Denko Corporation as a column. 804L / K-804L can be measured using chloroform or the like as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

In combination with (B) active ester compound, (C) carbodiimide compound, and a certain amount or more of (E) inorganic filler, any of dielectric positive contact, thermal expansion rate, breaking point elongation, surface roughness and peel strength. From the viewpoint of obtaining an insulating layer having excellent properties, particularly from the viewpoint of obtaining an insulating layer having high peel strength, the thermoplastic resin is one or more atoms or carbons selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms. It is preferable to have a functional group containing a carbon double bond. Such functional groups include hydroxyl groups, carboxy groups, acid anhydride groups, epoxy groups, amino groups, thiol groups, enol groups, enamine groups, urea groups, cyanate groups, isocyanate groups, thioisocyanate groups, diimide groups and alkenyl groups. , One or more selected from the group consisting of an Allen group and a Keten 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 functional groups, the functional group equivalent of the thermoplastic resin is preferably 100,000 or less, more preferably 90,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, 30,000 or less, 20000 or less, 10000 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 can usually be 50 or more, 100 or more, and the like.

The suitable thermoplastic resin will be described in more detail below, but a thermoplastic resin in which the above-mentioned functional group is further added to the thermoplastic resin shown below can also be preferably used in the present invention according to a known procedure. ..

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen. Examples thereof include a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (both manufactured by Mitsubishi Chemical Corporation). Bisphenol acetophenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL7553", "YL6794", "YL7213" manufactured by Mitsubishi Chemical Corporation, Examples thereof include "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 and BX series manufactured by Sekisui Chemical Co., Ltd. Examples include the KS series (for example, KS-1), the BL series, and the BM series.

The acid anhydride group-containing vinyl resin can be obtained, for example, by copolymerizing an acid anhydride group-containing monomer (d1) with 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 is an ethylenically unsaturated monomer 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 VALLY HSC.

Specific examples of the polyimide resin include "Rikacoat SN-20" and "Rikacoat PN-20" manufactured by Shin Nihon Rika Co., Ltd., and "Unidic V-8000" manufactured by DIC Co., Ltd. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083), and a polysiloxane skeleton-containing polyimide (Japanese Patent Laid-Open No. 2006-37083). Examples thereof include modified polyimides such as JP-A-2002-12667, JP-A-2000-319386, WO2010 / 53186, etc.).

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

Examples of the styrene-based elastomer resin include block copolymers containing a block of styrene or an analog thereof as at least one terminal block and an elastomer block of a conjugated diene or its hydrogenated product as at least one intermediate block. Can be done. Specifically, styrene-butadiene diblock copolymer, styrene-butadiene triblock copolymer, styrene-isopregen block copolymer, styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene triblock copolymer, Examples thereof include hydrogenated styrene-isopregen block copolymer, hydrogenated styrene-isoprenetriblock copolymer, hydrogenated styrene-butadiene random copolymer and the like. Specific examples of the styrene-based elastomer resin include Asaprene, Toughprene, and Asaflex manufactured by Asahi Kasei Kogyo Co., Ltd .; Hybler 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 polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

In combination with (B) active ester compound, (C) carbodiimide compound, and a certain amount or more of (E) inorganic filler, any of dielectric positive contact, thermal expansion rate, breaking point elongation, surface roughness and peel strength. From the viewpoint of obtaining an insulating layer having excellent properties, the content of the thermoplastic resin in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more. 2, 2% by mass or more is more preferable. 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, further 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) active ester compound, (C) carbodiimide compound, and (D) thermoplastic resin, it is excellent in all properties of dielectric loss tangent, coefficient of thermal expansion, break point elongation, 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 50% by mass or more, still more preferably 55% by mass or more or 60% by mass or more. In the present invention in which the 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, surface roughness and peel strength are reduced. However, 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. You can raise it 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, still more preferably 80% by mass or less, from the viewpoint of the mechanical strength of the obtained insulating layer. ..

The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconate oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate zirconate, zirconate titnzate phosphate and the like, and silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SO-C2" and "SO-C1" manufactured by Admatex Co., Ltd.

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

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent. It is preferable that the treatment is performed with one or more surface treatment agents such as. Commercially available surface treatment agents include, for example, "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. Examples thereof include "SZ-31" (hexamethyldisilazane) manufactured by Co., Ltd.

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

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

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

The curing accelerator is not particularly limited, and examples thereof include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, guanidine-based curing accelerators, and amine-based curing accelerators and imidazole-based curing agents. 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. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

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

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Above all, as a curing accelerator, 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 in combination with the above components (A) to (E), the curing accelerator is used. 4-Dimethylaminopyridine and 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>
-Hardener-
The resin composition of the present invention may further contain a curing agent (however, the component (B) is excluded). By containing a curing agent, the insulation reliability, peel strength, and mechanical strength of the obtained insulating layer can be enhanced. 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 agent may be used alone or in combination of two or more. Among these, a phenolic curing agent 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 in combination with the above components (A) to (E). , Naftor-based curing agent and cyanate ester-based curing agent are preferable.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of peel strength, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with the 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 Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", manufactured by Nippon Steel & Sumitomo Metal Corporation, "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090" manufactured by DIC Co., Ltd. , Etc. can be mentioned.

The cyanate ester-based curing agent is not particularly limited, and for example, a novolak type (phenol novolac type, alkylphenol novolac type, etc.) cyanate ester-based curing agent, a dicyclopentadiene type cyanate ester-based curing agent, a bisphenol type (bisphenol A type, etc.) Examples thereof include bisphenol F type, bisphenol S type, etc.) cyanate ester-based curing agents, and prepolymers in which these are partially triazined. Specific examples include bisphenol A disicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis (2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl. Disianate, Hexafluorobisphenol A Disianate, 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 novolac and cresol novolac. Examples thereof include a polyfunctional cyanate resin derived from the above, a prepolymer in which these cyanate resins are partially triazined, and the like. Commercially available cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins) and "BA230" (part or all of bisphenol A disocyanate) manufactured by Lonza Japan Co., Ltd. Is a prepolymer that has been triadinated to form a trimer) and the like.

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

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, 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 an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more. 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 they are fine particles of a resin that is chemically crosslinked with a resin exhibiting rubber elasticity and is insoluble and insoluble in an organic solvent. For example, acrylonitrile butadiene rubber particles, butadiene rubber particles, and the like. Examples include acrylic rubber particles. Specific examples of the rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by Aica Kogyo Co., Ltd.) Pararoid EXL2655. , EXL2602 (all manufactured by Kureha Chemical Industry Co., Ltd.) and the like.

The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, 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 by mass using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by creating a standard and using the median diameter as the average particle size. 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, if necessary. Such other components include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, as well as thickeners, defoaming agents, leveling agents, adhesion-imparting agents, colorants and curable resins. Such as resin additives 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 a compounding component is mixed and dispersed using a rotary mixer or the like by adding a solvent or the like as necessary.

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 in <Measurement of Dissipation Factor> described later. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the 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 0.010 or less, more preferably 0.009 or less, and 0.008 or less, 0.007 or less or 0.006 or less. More preferred. The lower limit of the dielectric loss tangent is preferably as low as possible, but 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 in <Measurement of glass transition temperature and coefficient of linear thermal expansion> described later. Specifically, the average linear thermal expansion coefficient in the plane direction at 25 to 150 ° C. can be measured by performing thermomechanical analysis by the tensile weighting method. The cured product of the resin composition of the present invention is preferably 40 ppm / ° C. or lower, more preferably 35 ppm / ° C. or lower, still more preferably 30 ppm / ° C. or lower, still more preferably 25 ppm / ° C. or lower, and particularly preferably 20 ppm / ° C. or lower. The coefficient of linear thermal expansion of can be shown. The lower limit of the coefficient of linear thermal expansion is not particularly limited, but is usually 1 ppm / ° C. or higher.

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

The resin composition of the present invention can provide a cured product (insulating layer) having a low surface roughness. The arithmetic mean roughness (Ra) of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of Arithmetic Mean Roughness (Ra)> described later. It is desirable that the surface of the insulating layer after the roughening treatment has small surface irregularities in terms of reducing the loss of electrical signals. Specifically, the arithmetic average roughness (Ra) of the surface of the insulating layer after the resin composition is cured to form the insulating layer and the surface of the insulating layer is roughened is preferably 140 nm or less, preferably 130 nm. The following is more preferable, 120 nm or less is further preferable, 110 nm or less is even more preferable, and 100 nm or less is particularly preferable. The lower limit of the arithmetic mean roughness (Ra) is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, from the viewpoint of obtaining sufficient peel strength.

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 in <Measurement of Peel Strength of Plated Conductor Layer> described later. Specifically, when the resin composition is cured to form an insulating layer and the surface of the insulating layer is roughened and then plated to form a conductor layer, the peel between the obtained conductor layer and the insulating layer is obtained. The strength is preferably 0.50 kgf / cm or more, more preferably 0.55 kgf / cm or more, and even more preferably 0.60 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but usually, it may be 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 in <Measurement of Breaking Point Elongation> described later. The cured product of the resin composition of the present invention can preferably exhibit a glass transition temperature (Tg) of 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), and an interlayer insulating layer of the printed wiring board. It can be more preferably used as a resin composition for forming an interlayer insulating layer (resin composition for an interlayer insulating layer of a printed wiring board), and for forming an interlayer insulating layer on which a conductor layer is formed by plating. It can be more preferably used as a resin composition (a resin composition for an interlayer insulating layer of a printed wiring board that forms a conductor layer 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 encapsulant, a hole filling resin, and a component embedding resin. Can be used in a wide range of applications.

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

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, still more 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 a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples include ketones and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The surface of the support on the side to be joined with the resin composition layer may be matted or corona-treated. Further, as the support, a support with a release layer having a release layer on the surface on the side to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, olefin resin, urethane resin, and silicone resin. .. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based 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 in the above range.

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

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

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

In the adhesive film, a protective film similar 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 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 scratches. The adhesive film can be rolled up and stored. If 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 (printed wiring board). A resin composition for forming an interlayer insulating layer (for an interlayer insulating layer formed by plating) on which a conductor layer is formed by plating (interlayers of a printed wiring board on which a conductor layer is formed by plating). It can be more preferably used for an insulating layer).

[Printed circuit board]
The printed wiring board of the present invention includes an insulating layer formed of 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) A step of laminating an adhesive film on an inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer.

The "inner layer substrate" used in the step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, or the like, or one or both sides of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, the inner layer circuit board of the intermediate product in which the insulating layer and / or the conductor layer should be further formed when the printed wiring board is manufactured is also included in the "inner layer board" in the present invention.

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

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

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

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

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

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

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

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

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

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

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

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

The 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 conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed of a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single copper layer is preferable. A metal layer is more preferred.

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

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

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

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

As described above, by manufacturing a printed wiring board using the resin composition of the present invention, an insulating layer having excellent properties of dielectric loss tangent, coefficient of thermal expansion, elongation at break, surface roughness and peel strength is excellent. It is possible to advantageously manufacture a printed wiring board provided with the above.

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

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

The method for mounting a semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" means mass part.

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

<Preparation of sample for measuring peel strength and arithmetic mean roughness (Ra value)>
(1) Base treatment of inner layer circuit board Glass cloth base material with inner layer circuit Epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation “R1515A”) Both sides of the copper surface were roughened by etching 1 μm with “CZ8101” manufactured by MEC Co., Ltd.

(2) Lamination of Adhesive Films The adhesive films produced in Examples and Comparative Examples are subjected to an inner layer circuit with a resin composition layer using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). Both sides of the inner layer circuit board were laminated so as to be bonded to the substrate. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

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

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

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

<Measurement of Arithmetic Mean Roughness (Ra)>
For the evaluation substrate a, the Ra value was determined by the numerical value obtained with the measurement range of 121 μm × 92 μm by the VSI contact mode and the 50x lens using a non-contact type surface roughness meter (“WYKO NT3300” manufactured by Becoin Sturments). .. It was measured by calculating the average value of 10 randomly selected points.

<Measurement of peel strength of plated conductor layer>
The peel strength of the insulating layer and the conductor layer was measured for the evaluation substrate b in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, a notch having a width of 10 mm and a length of 100 mm is made in the conductor layer of the evaluation substrate b, one end of the notch is peeled off, and the conductor layer is grasped with a gripper. The load (kgf / cm) when the 35 mm was peeled off was measured, and the peeling strength was determined. A tensile tester (“AC-50C-SL” manufactured by TSE Co., Ltd.) was used for the measurement.

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

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

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

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

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

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

<Example 3>
100 parts of spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatex Co., Ltd.) 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 above was changed to.

<Example 4>
Aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 275 parts of spherical silica (average particle size 0.5 μm, "SO-C2" manufactured by Admatex Co., Ltd.) Except for changing to 275 parts of spherical silica (average particle size 0.3 μm, "SO-C1" manufactured by Admatex Co., Ltd.) surface-treated with a coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573"). , A resin varnish and an adhesive film were produced in the same manner as in Example 1.

<Example 5>
20 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Co., Ltd., an active group equivalent of about 223, a toluene solution of 65% by mass of a non-volatile component) was added to an active ester compound (“EXB9050L-62M” manufactured by DIC 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 21 parts (MEK solution having an active group equivalent of about 334 and a non-volatile component of 62% by mass).

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

<Example 7>
20 parts of carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., toluene solution of 50% by mass of non-volatile component), carbodiimide compound (“V-07” manufactured by Nisshinbo Chemical Co., Ltd., NCO content 0.5 mass) A resin varnish and an adhesive film were produced in the same manner as in Example 1 except that the amount was changed to 20 parts (toluene solution of 50% by mass of non-volatile component).

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

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

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

<Example 11>
20 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass), polyimide resin ("Unidic V-8000" manufactured by DIC Corporation, non-volatile component A resin varnish and an adhesive film were prepared in the same manner as in Example 1 except that the solution was changed to 15 parts (40 mass% ethyldiglycol acetate solution).

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

<Example 13>
The amount of the triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Co., Ltd., hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%) was changed to 5 parts, and the benzoxazine type was changed. 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 (“Pd” manufactured by Shikoku Kasei Kogyo Co., Ltd., a cyclohexanone solution having a solid content of 50%) was added.

<Example 14>
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) was added to the siloxane skeleton-containing polyimide resin (solid content 55% by mass) of Synthesis Example 1. A resin varnish and an adhesive film were produced in the same manner as in Example 2 except that the number was changed to 9.

[Synthesis Example 1]
20 parts of 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA) in a 500 mL separable flask equipped with a water metering receiver connected with a recirculation cooler, a nitrogen introduction tube, and a stirrer. 70.9 parts of γ-butyrolactone, 7 parts of toluene, 61.5 parts of diaminosiloxane (“X-22-9409” manufactured by Shinetsu Chemical Industry 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 reaction was carried out by stirring at 45 ° C. for 2 hours under a nitrogen stream. rice field. Next, the temperature of this reaction solution was raised, and condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. After confirming that a predetermined amount of water had accumulated in the water content metering receiver and that no outflow of water was observed, the temperature was further raised and the mixture was stirred at 200 ° C. for 1 hour. After that, it was cooled to finish, and a varnish containing 55% by mass of a siloxane skeleton-containing polyimide resin having a hexafluoroisopropanol group (HFA group) was prepared. In this case, the content of the siloxane structure in the resin is 70.9% by mass, and the HFA group equivalent is 2881 g / mol.

<Example 15>
Changed 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 180) to 10 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 235). A resin varnish and an adhesive film were produced in the same manner as in Example 1.

<Comparative example 1>
A resin varnish and an adhesive film were prepared in the same manner as in Example 1 except that 20 parts of a carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution having a non-volatile component of 50% by mass) was not used.

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

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

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

The results are shown in Table 1.

Claims (1)

It contains (A) epoxy resin, (B) active ester compound, (C) carbodiimide compound, (D) thermoplastic resin and (E) inorganic filler, and the content of (E) component is non-volatile in the resin composition. A resin composition which is 40% by mass or more when the component is 100% by mass.