KR20160150587A - Resin composition - Google Patents

Abstract

Provided is a resin composition capable of forming insulation layers with outstanding properties such as fracture point elongation, dielectric tangent, and circuit embedding properties when producing printed circuit boards. Also, provided are an adhesive film using the same, a printed circuit board, and a semiconductor device. To this end, the resin composition comprises (A) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole which may have a substituent.

Description

Resin composition {RESIN COMPOSITION}

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

As a manufacturing method of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately laminated is known. In the build-up method, generally, the insulating layer is formed by curing the resin composition.

For example, Patent Document 1 discloses a resin composition containing a hydroxyl group-containing silicone compound (A), a cyanate ester compound (B) and / or a phenol resin (C) and an inorganic filler (D).

Patent Document 1: JP-A-2014-84327

The resin composition of Patent Document 1 discloses that it maintains high flame retardancy by curing, has high heat resistance, low coefficient of thermal expansion in the plane direction, and excellent drilling workability. However, various characteristics that are important in the production of a printed wiring board are not satisfactorily balanced and are insufficient.

The present invention provides a resin composition capable of forming an insulating layer having any of the characteristics of circuit embedding property, dielectric tangent property and breaking point elongation at the time of manufacturing a printed wiring board, an adhesive film using the same, a printed wiring board and a semiconductor device .

As a result of intensive studies on the above problems, the inventors of the present invention found that (A) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole, which may have a substituent, The present invention has been accomplished on the basis of these findings.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole which may have a substituent.

[2] The resin composition according to claim 1, wherein the content of the component (B) is 1% by mass to 30% by mass based on 100% by mass of the nonvolatile component in the resin composition.

[3] The resin composition according to any one of claims 1 to 5, wherein the content of the component (C) is 0.01% by mass to 5% by mass based on 100% by mass of the nonvolatile component in the resin composition.

[4] The resin composition according to any one of claims 1 to 3, which comprises (D) an inorganic filler.

[5] The resin composition according to claim 4, wherein the content of the component (D) is 50% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

[6] The resin composition according to any one of claims 4 to 5, wherein the component (D) has an average particle diameter of 0.01 탆 to 3 탆.

[7] The resin composition according to any one of claims 4 to 6, wherein the component (D) is silica.

[8] The resin composition according to any one of claims 1 to 7, which comprises (E) a thermoplastic resin.

[9] An adhesive film having a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 8 formed on the support.

[10] The adhesive film according to claim 9, wherein the minimum melt viscosity of the resin composition layer is 3000 poise or less.

[11] The adhesive film according to claim 9 or 10, wherein the cured resin composition layer has a breaking point elongation of 1.5% or more.

[12] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 8.

[13] A semiconductor device comprising the printed wiring board according to claim 12.

According to the present invention, there is provided a resin composition capable of forming an insulating layer having excellent characteristics such as circuit embedding property, dielectric loss tangent and breaking point elongation at the time of manufacturing a printed wiring board, an adhesive film using the same, a printed wiring board and a semiconductor device .

Hereinafter, the resin composition, the adhesive film, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

[Resin composition]

The resin composition of the present invention is characterized by containing (A) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole which may have a substituent. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

≪ (A) Epoxy resin >

The resin composition of the present invention contains (A) an epoxy resin (hereinafter also referred to as component (A)).

Examples of the epoxy resin include epoxy resins such as 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, Epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexanedimethanol type epoxy resins, Tylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane type epoxy There may be mentioned resins, the beak nolhyeong silane and epoxy resins. The epoxy resin may be used singly or in combination of two or more kinds.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more of the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule. Among them, epoxy resins having two or more epoxy groups in one molecule and having a liquid epoxy resin (hereinafter referred to as " liquid epoxy resin ") at a temperature of 20 캜 and three or more epoxy groups in one molecule, (Hereinafter referred to as " solid epoxy resin "). By using a liquid epoxy resin and a solid epoxy resin as an epoxy resin in combination, a resin composition having excellent flexibility can be obtained. Further, the fracture 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, alicyclic epoxy Resin and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin and a naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin), "828US" and "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Kagaku ), "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd. (bisphenol A type epoxy resin and bisphenol F type epoxy resin EX-721 " (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., " Celloxide 2021P " (alicyclic epoxy resin having ester skeleton) manufactured by Daicel Co., , &Quot; PB-3600 " (epoxy resin having a butadiene structure). These may be used singly or in combination of two or more kinds.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins , An anthracene type epoxy resin, a bisphenol A type epoxy resin and a tetraphenylethane type epoxy resin are preferable, and a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin and a biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include HP-4032H (naphthalene type epoxy resin), HP-4700, HP-4710 (naphthalene type tetrafunctional epoxy resin), and N-690 (Cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "EXA7311" EPPN-502H "(trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.," EPA7311-G4 "," EXA7311-G4S "," HP-6000 "(naphthylene ether type epoxy resin) , "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., (Naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YX4000HK "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" manufactured by Mitsubishi Kagaku Co., Ltd. Quot; jER1010 " (solid bisphenol A type epoxy resin), " jER1031S " (tetraphenyl ethane type epoxy resin) and YL7760 (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation .

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is preferably in the range of 1: 0.1 to 1: 6 by mass ratio. By setting the proportions of the liquid epoxy resin and the solid epoxy resin in this range, it is possible to form suitable adhesiveness in the case of i) use in the form of an adhesive film, and ii) to obtain flexibility when used in the form of an adhesive film And the handling property is improved, and (iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 0.3 to 1: 5, : 0.6 to 1: 4 is more preferable.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability to be. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

In the present invention, the content of each component in the resin composition is a value obtained by assuming that the nonvolatile 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, still more preferably 110 to 1000. With this range, the crosslinked density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of the resin containing one equivalent of epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

≪ (B) Active ester compound >

The resin composition of the present invention contains (B) an active ester compound (hereinafter also referred to as component (B)).

The active ester compound is an active ester compound having at least one active ester group in one molecule. The active ester compound is preferably an active ester compound having two or more active ester groups in one molecule, and examples thereof include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds An active ester compound having two or more ester groups having a high reaction activity such as an alkyl group or the like is preferably used. The active ester compound may be used singly or in combination of two or more kinds.

From the viewpoint of improvement in heat resistance, an active ester compound obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with at least one selected from a phenol compound, a naphthol compound and a thiol compound is more preferable, and an active ester compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group , An aromatic compound having at least two active ester groups per molecule is more preferable and as the aromatic compound obtained by reacting a carboxylic acid compound having at least two carboxyl groups in one molecule with an aromatic compound having a phenolic hydroxyl group, And still more preferably an aromatic compound having at least two active ester groups. The active ester compound may be in a linear form or in a branched form. In addition, if the carboxylic acid compound having at least two carboxyl groups in one molecule contains an aliphatic chain, compatibility with the resin composition can be enhanced, and heat resistance can be enhanced if the compound has an aromatic ring.

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

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

Examples of the phenol compound include a phenol compound having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and still more preferably 6 to 22) carbon atoms, Methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzene, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol, and the like. As the phenol compound, a phenol novolak, a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 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) carbon atoms, and specific examples include? -Naphthol,? -Naphthol, Dihydroxynaphthalene, 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, alpha -naphthol, beta -naphthol, 1,5- dihydroxynaphthalene, Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol, phenol novolac, And phosphorus atom-containing oligomers having a phenolic hydroxyl group are preferable, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Containing oligomers having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, - Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenol, phenol novolak, phenol novolak, phenol novolak, And a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol , Phenol novolac, and phosphorus atom-containing oligomers having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopenta Diene-type diphenols, phosphorus atom-containing oligomers having a phenolic hydroxyl group are even more preferred, and dicyclopentadiene-type diphenols are particularly preferred.

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

Suitable specific examples of the active ester compound include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolak, benzoyl phenol novolak An active ester compound containing an aromatic carboxylic acid and a phosphorus atom-containing oligomer having a phenolic hydroxyl group. 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 and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable. In the present invention, the "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit comprising phenylene-dicyclopentylene-phenylene.

As the active ester compound, the active ester compound disclosed in JP-A-2004-277460 or JP-A-2013-40270 may be used, or a commercially available active ester compound may be used. Examples of commercial products of the active ester compound include EXB9451, EXB9460, EXB9460S, HPC-8000-65T, HPC-8000L-65M EXB9416-70BK " (an active ester compound containing a naphthalene structure) manufactured by DIC Corporation, " DC808 " (phenol novolac acetyl YLH1026 "(active ester compound containing phenol novolak benzoylate) manufactured by Mitsubishi Chemical Corporation," EXB9050L-62M "(product containing phosphorus atoms Active ester compounds).

The content of the active ester compound in the resin composition is preferably at least 1% by mass, more preferably at least 2% by mass, further preferably at least 3% by mass, more preferably at least 4% by mass, at least 5% Or even more preferably 7% by mass or more. The upper limit of the content of the active ester compound is not particularly limited, but is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less, further preferably 15 mass% or less, or 10 mass% .

When the epoxy group number of the epoxy resin (A) is 1, the number of reactors of the active ester compound (B) is preferably 0.1 to 2, more preferably 0.2 to 1.5, in view of obtaining an insulating layer having a good mechanical strength More preferably from 0.3 to 1. Here, the "epoxy group number of the epoxy resin" is a value obtained by dividing the value obtained by dividing the solid content of each epoxy resin present in the resin composition by the epoxy equivalent, for all epoxy resins. The term " reactor " means a functional group capable of reacting with an epoxy group, and the " number of reactors of active ester compound " is a total value obtained by dividing the solid content of the active ester compound present in the resin composition by the equivalent of the reactor .

<(C) Triphenylimidazole which may have a substituent>

The resin composition of the present invention contains triphenyl imidazole (hereinafter also referred to as component (C)) which may have a substituent (C) as a curing accelerator.

The inventors of the present invention have found that when a component (B) and a component (C) are used in combination in a resin composition, an excellent insulating layer is formed in any of the circuit embedding property, dielectric tangent property and breaking point elongation . This is because the curing reaction of the component (A) and the component (B) is delayed because the phenyl group in the component (C) is a rigid substituent and the curing reaction of the component (A) And the viscosity is likely to be lowered. In the conventional curing accelerator, when the content of the inorganic filler is large, the melt viscosity becomes high and the circuit filling property tends to decrease. In the present invention, however, the melt viscosity can be kept low by using the component (C) Can be achieved.

In the present specification, "triphenyl imidazole which may have a substituent" refers to triphenyl imidazole in which a hydrogen atom thereof is not substituted with a substituent, and triphenyl imidazole in which a part or all of hydrogen atoms thereof are substituted with a substituent It means both. When the triphenyl imidazole has a substituent, the hydrogen atom at the 1-position of the imidazole may be substituted with a substituent, or the hydrogen atom of the phenyl group may be substituted with a substituent.

The substituent is not particularly limited, for example, a halogen atom, -OH, -OC _{1 - 6} alkyl, -N (C _{1 - 6} alkyl) _2, C _{1 - 6} alkyl, C _{6 - 10} aryl group, - there may be mentioned ₆ alkyl, -COOH, -C (O) H , -NO 2 and so on _{- NH 2, -CN, -C (} O) OC 1.

Here, the term "C _{p -q} " (p and q are positive integers and p <q is satisfied) indicates that the number of carbon atoms of the organic group (organic group) described immediately after this term is p to q . For example, "C _{1 - 6} alkyl group" term represents an alkyl group of 1 to 6 carbon atoms.

The above-mentioned substituent may further have a substituent (hereinafter may be referred to as &quot; secondary substituent &quot;). As the secondary substituent, the same substituents as those described above may be used, unless otherwise specified.

Among these, as the component (C), triphenyl imidazole in which the hydrogen atom at the 1-position of the imidazole or the hydrogen atom of the phenyl group is not substituted by a substituent is preferable, and 2,4,5-triphenyl imidazole is more preferable .

The content of the component (C) is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, still more preferably 0.05 mass% or more, or 0.1 mass% or more. The upper limit of the content of the component (C) is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 2% Or less.

C / b is in the range of 0.001 to 0.2 (mass%) when the content of the component (B) is b (mass%) and the content of the component (C) More preferably 0.005 to 0.1, and still more preferably 0.01 to 0.05.

<(D) Inorganic filler>

The resin composition of the present invention preferably contains, in addition to the components (A) to (C), (D) an inorganic filler (hereinafter also referred to as component (D)).

The material of the inorganic filler is not particularly limited and may be, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Magnesium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , Barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is not particularly limited. However, from the viewpoint of obtaining an insulating layer with a small surface roughness and improving the fine wiring formation property, the average particle diameter is preferably 3 mu m or less, more preferably 2 mu m or less, Is not more than 1 mu m. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 占 퐉 or more, more preferably 0.1 占 퐉 or more, and still more preferably 0.3 占 퐉 or more. Examples of commercially available inorganic fillers having such an average particle diameter include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomex Corporation, "YA010C" manufactured by Denki Kagakukogyo Co., UF-30 "manufactured by Tokuyama Corporation," Silpol NSS-3N "," Silpol NSS-4N "," Silpol NSS-5N "manufactured by Tokuyama Corporation," SO- And the like.

The average particle directness of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured by using a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter of the inorganic filler is determined as the average particle diameter. The measurement sample can be preferably those in which an inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is preferably selected from the group consisting of an amino silazane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, an alkoxysilane compound, an organosilazane compound and a titanate coupling agent It is preferable that the surface treatment agent is treated with at least two kinds of surface treatment agents. As commercially available products of surface treatment agents, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercapto KBM903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM573 "(manufactured by Shin-Etsu Chemical Co., SZ-31 (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM103 (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin- KBM-4803 &quot; (long-chain epoxy type silane coupling agent).

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably at least 0.02 mg / m 2, more preferably at least 0.1 mg / m 2, and most preferably at least 0.2 mg / m 2 from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, still more preferably 0.5 mg / m 2 or less from the viewpoint of preventing the melt viscosity of the resin varnish and the increase of the melt viscosity in the sheet form.

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 Is added to the inorganic filler surface-treated with a surface treatment agent and ultrasonically cleaned at 25 DEG C for 5 minutes. After the supernatant is removed and the solid content is dried, the amount of carbon per unit surface area of the inorganic filler is measured using a carbon analyzer As the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

The content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more from the viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion. The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, or 80% by mass or less, Or less.

&Lt; (E) Thermoplastic Resin>

The resin composition of the present invention preferably contains a thermoplastic resin (hereinafter also referred to as component (E)) in addition to the components (A) to (C).

Examples of the thermoplastic resin include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, Ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins. Phenoxy resins are preferred. The thermoplastic resin may be used singly or in combination of two or more.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K (manufactured by Showa Denko K.K. -804L / K-804L as a mobile phase, chloroform at a column temperature of 40 占 폚, and using a calibration curve of standard polystyrene.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used singly or in combination of two or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" (Phenoxy resin containing bisphenol acetophenone skeleton), and "FX280" and "FX293" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., "YX6954BH30" and "YX7553" manufactured by Mitsubishi Chemical Corporation YL7591BH30 "," YL7769BH30 "," YL6794 "," YL7213 "," YL7290 "," YL7891BH30 ", and" YL7482 "

As the polyvinyl acetal resin, for example, a polyvinyl formal resin and a polyvinyl butyral resin can be mentioned, and a polyvinyl butyral resin is preferable. As specific examples of the polyvinyl acetal resin, there may be mentioned, for example, &quot; Phone Butyral 4000-2 &quot;, &quot; Phone Butyral 5000-A &quot;, &quot; Phone Butyral 6000- Butyral 6000-EP &quot;, S-LEC BH series, BX series, KS series, BL series, BM series manufactured by Sekisui Kagakukogyo Co., Ltd., and the like.

Specific examples of the polyimide resin include "Rika coat SN20" and "Rika coat PN20" manufactured by Shin-Epson Lion Corporation. Specific examples of the polyimide resin include linear polyimide (polyimide described in JP-A 2006-37083) obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, Modified polyimides such as polysiloxane skeleton-containing polyimide (Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.).

Specific examples of the polyamide-imide resin include "Bioromax HR11NN" and "Bioromax HR16NN" manufactured by Toyoboseki KK. Specific examples of the polyamide-imide resin include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Kasei Corporation.

Specific examples of the polyethersulfone resin include "PES 5003P" manufactured by Tsumito Tomokagaku Co., Ltd. and the like.

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

Specific examples of the polyphenylene ether resin include an oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like.

Among them, a phenoxy resin and a polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in a preferred embodiment, the component (E) comprises at least one member selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and still more preferably 1% by mass to 5% by mass.

<Other additives>

The resin composition of the present invention may contain other additives as required. Other additives include a curing agent other than the component (B), a curing accelerator other than the component (C), a flame retardant, and an organic filler.

- a curing agent other than the component (B)

The resin composition of the present invention may further contain a curing agent (hereinafter also referred to as component (F)) other than the component (B).

The component (F) is not particularly limited as long as it has a function of curing the epoxy resin. Examples of the component (F) include a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, a benzoxazine-based curing agent and a carbodiimide- . These curing agents may be used singly or in combination of two or more kinds.

Among them, a phenol-based curing agent and a naphthol-based curing agent are preferable as the component (F) from the viewpoint of obtaining an insulating layer exhibiting good elongation at break in combination with the components (A) to (C).

As the phenol-based curing agent and 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 viewpoints of heat resistance and water resistance. From the viewpoint of obtaining an insulating layer having excellent peel strength from the conductor layer, a nitrogen-containing phenol-based curing agent and a nitrogen-containing naphthol-based curing agent are preferable, and a triazine skeleton-containing phenol-based curing agent and a triazine skeleton- desirable. Of these, phenol novolac resins containing a triazine skeleton and naphthol novolac resins containing a triazine skeleton are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and peel strength with a conductor layer. Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., SN-180 "," SN-190 "," SN-475 "and" SN-485 "manufactured by Shinnitetsu Sumikin Kagaku Co., LA-7054 "," LA-3018 "," LA-1356 "," SN-395 " &Quot; TD2090 &quot;, and the like.

Examples of the cyanate ester curing agent include, but are not limited to, cyanate ester curing agents such as novolak type (phenol novolac type, alkylphenol novolac type and the like), dicyclopentadiene type cyanate ester type curing agents, bisphenol type (Bisphenol A type, bisphenol F type, bisphenol S type and the like) cyanate ester type curing agents, and prepolymer obtained by partially trimerizing them. Specific examples thereof include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2,6-dimethyl phenyl cyanate) Bis (4-cyanatophenylmethane), bis (4-cyanatophenyl) methane, and the like. Benzene, bis (4-cyanate phenyl) thioether, and bis (4-cyanate-3,5-dimethylphenyl) (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolak, and prepolymers obtained by partially triarizing these cyanate resins. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolak-type multifunctional cyanate ester resins) manufactured by RONJANJANPAN CO., LTD., "BA230" (part or all of bisphenol A dicyanate And a prepolymer obtained by trimerization to give a trimer).

Specific examples of the benzoxazine type curing agent include "HFB2006M" manufactured by Showa Kobunshi Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Seiko Kogyo Co.,

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

When the component (F) is used, the content of the curing agent in the resin composition is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, still more preferably 0.7% by mass or more, or 1% . The upper limit of the content is preferably 10 mass% or less, more preferably 8 mass% or less, 4 mass% or less, 3 mass% or less, or 2 mass% or less.

- Curing accelerator other than component (C)

The resin composition of the present invention may further contain a curing accelerator (hereinafter also referred to as (G) component) other than the component (C).

Examples of the component (G) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators and metal-based curing accelerators. ), And it is more preferable to use an imidazole-based curing accelerator other than the amine-based curing accelerator and the component (C). The curing accelerator may be used singly or in combination of two or more kinds.

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

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

Examples of the imidazole-based curing accelerator other than the component (C) include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1- 2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- ] -Ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] Phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, Methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenyl-1,3-dihydro-1H- pyrrolo [ Imidazole compounds such as imidazole and imidazole compounds and adducts of epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, commercially available products may be used. Examples thereof include &quot; P200-H50 &quot; manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [ 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferred.

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

The content of the component (G) in the resin composition is not particularly limited, but is preferably in the range of 0.05% by mass to 3% by mass.

- Flame retardant -

The resin composition of the present invention may contain a flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon-based flame retardants, metal hydroxides and the like. The flame retardant may be used alone, or two or more flame retardants may be used in combination.

As the flame retardant, a commercially available product may be used, for example, "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Daihachi Chemical Co.,

The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and still more preferably 1.5% by mass to 10% by mass.

- Organic filler -

The resin composition may further include an organic filler (hereinafter also referred to as component (H)) from the viewpoint of improving the drawing. As the component (H), any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

As the rubber particles, a commercially available product may be used, and for example, "EXL-2655" manufactured by Dow Chemical Co., Ltd. and "AC3816N" manufactured by AIKA CO., LTD.

The content of the component (H) in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, further preferably 0.3% by mass to 5% 3% by mass.

The resin composition may further contain other additives as required. Examples of such other additives include organometallic compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, organic fillers such as organic fillers, thickeners, Defoaming agents, leveling agents, adhesion-imparting agents, and resin additives such as coloring agents.

The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 130 占 폚 or higher, more preferably 150 占 폚 or higher, even more preferably 155 占 폚 or higher, or 160 占 폚 or higher. The upper limit is preferably 200 占 폚 or lower, more preferably 190 占 폚 or lower, and even more preferably 180 占 폚 or lower. The glass transition point (Tg) of the cured product of the resin composition can be measured by thermomechanical analysis using a tensile weighting method (JIS K7197) using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation) .

The elongation at break of the cured product of the resin composition of the present invention is preferably 1.5% or more, more preferably 1.6% or more, more preferably 1.7% or more, 1.8% or more, 1.9% or more, or 2.0% or more Do. The upper limit of the breaking point elongation is preferably as high as possible, but usually it may be 5% or less. The elongation at break of the cured product of the resin composition can be measured by the method described in &quot; Measurement of elongation at break &quot;

The dielectric loss tangent of the cured product of the resin composition of the present invention is preferably 0.02 or less, more preferably 0.01 or less, still more preferably 0.009 or less or 0.008 or less. The lower limit of the dielectric tangent is preferably as low as possible, but may be usually 0.001 or more. The dielectric loss tangent of the cured product of the resin composition can be measured by the method described in &quot; Measurement after dielectric loss tangent &quot;

The resin composition of the present invention can form an insulating layer excellent in any of the characteristics of circuit embeddability, dielectric tangent, and break point elongation at the time of manufacturing a printed wiring board. Therefore, the resin composition of the present invention can be suitably used as a resin composition (resin composition for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and can be used as a resin composition for forming an interlayer insulating layer of a printed wiring board (For example, a resin composition for an interlaminar insulating layer). The resin composition of the present invention can also be suitably used as a solder resist.

[Adhesive film]

The adhesive film of the present invention is characterized by having a support and a resin composition layer formed on the support and comprising the resin composition of the present invention.

The thickness of the resin composition layer is preferably 100 占 퐉 or less, more preferably 80 占 퐉 or less, still more preferably 60 占 퐉 or less, still more preferably 50 占 퐉 or less or 40 占 퐉 or less to be. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 占 퐉 or more, 5 占 퐉 or more, 10 占 퐉 or more, or the like.

The minimum melt viscosity of the resin composition layer is preferably not more than 3000 poise (300 Pa · s), more preferably not more than 2500 poise (250 Pa · s) and not more than 2000 Poise (200 Pa · s) More preferably not more than 1500 poise (150 Pa · s) or not more than 1000 poise (100 Pa · s). The lower limit of the lowest melt viscosity is preferably 100 poise (10 Pa · s) or higher, more preferably 200 poise (20 Pa · s) or higher, and still more preferably 250 poise (25 Pa · s) or higher.

The lowest melt viscosity of the resin composition layer means the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition is heated by heating at a constant heating rate to melt the resin, the melt viscosity of the resin is lowered with the temperature rise in the initial stage, and thereafter, the melt viscosity increases with the temperature rise. The lowest melt viscosity refers to the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method, and can be measured by, for example, the method described in &quot; Measurement of Minimum Melting Viscosity &quot;

As the support, for example, a film made of a plastic material, a metal foil and a release paper can be mentioned, and a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN" (Hereinafter may be abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. The copper foil may be a foil made of a single metal of copper or an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium or the like) A formed foil may be used.

The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment or a corona treatment.

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. As the release agent used for the release layer of the release layer-adhered support, for example, one or more release agents selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin can be mentioned. SK-1, &quot; &quot; AL-5, &quot; and &quot; SK-1 &quot; manufactured by Lintec Corporation, which are PET films having a releasing layer mainly composed of an alkyd resin-based releasing agent, AL-7 "manufactured by Toray Industries, Inc. and" Lumirror T6AM "manufactured by Toray Industries, Inc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 탆 to 75 탆, more preferably in the range of 10 탆 to 60 탆. When a release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

The adhesive film can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, coating the resin varnish on a support using a die coater or the like, and further drying the resin varnish to form a resin composition layer .

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. The organic solvent may be used singly or in combination of two or more kinds.

The drying may be carried out by a known method such as heating or hot air dispersion. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. For example, 30 to 60 mass% of the organic solvent is used, the resin varnish is dried at 50 to 150 DEG C for 3 to 10 minutes, A resin composition layer can be formed.

In the adhesive film, a protective film conforming to the support may be further laminated on the surface of the resin composition layer 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 탆 to 40 탆. By laminating a protective film, it is possible to prevent adhesion and scratching of dust or the like to the surface of the resin composition layer. The adhesive film can be rolled and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

The adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board) and more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board) Can be used.

[Printed circuit board]

The printed wiring board of the present invention is characterized by including an insulating layer formed by a cured product of the resin composition of the present invention.

For example, the printed wiring board of the present invention can be produced 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 the inner layer substrate and a resin composition layer of the adhesive film to be bonded to the inner layer substrate

(II) a step of thermally curing the resin composition layer to form an insulating layer

The term &quot; inner layer substrate &quot; used in the step (I) means a substrate mainly composed of a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, (Circuit) formed by patterning on one side (one side) or both sides of the circuit board. Further, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product to which an insulating layer and / or a conductor layer is to be further formed is also included in the &quot; inner layer board &quot; If the printed wiring board is a component built-in circuit board, an inner-layer board containing components may be used.

The lamination of the inner layer substrate and the adhesive film can be performed, for example, by thermally bonding an adhesive film to the inner layer substrate from the support side. Examples of the member for heating and pressing the adhesive film to the inner layer substrate (hereinafter, also referred to as "hot pressing member") include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). Further, it is preferable to press the heat-press member through an elastic material such as heat-resistant rubber such that the heat-press member is not pressed directly onto the adhesive film but the adhesive film sufficiently follows the surface unevenness of the inner-layer substrate.

The lamination of the inner layer substrate and the adhesive film may be performed by a vacuum lamination method. In the vacuum laminating method, the heat pressing temperature is preferably in the range of 60 占 폚 to 160 占 폚, more preferably 80 占 폚 to 140 占 폚, and the heat pressing pressure is preferably 0.098 MPa to 1.77 MPa, Preferably 0.29 MPa to 1.4 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure at a pressure of 26.7 hPa or less.

The lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meikishesakusho Co., Ltd., and a baking applicator manufactured by Nikko Materials Co., Ltd. can be given.

After lamination, the laminated adhesive film may be subjected to a smoothing treatment under atmospheric pressure (at atmospheric pressure), for example, by pressing the hot press member from the support side. The pressing condition of the smoothing treatment may be the same as the conditions of the hot pressing of the laminate. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing process may be performed continuously using the commercially available vacuum laminator.

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

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

The thermosetting condition of the resin composition layer is not particularly limited, and a condition that is generally adopted when forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting condition of the resin composition layer varies depending on the kind of the resin composition and the like, but the curing temperature is in the range of 120 to 240 占 폚 (preferably in the range of 150 to 220 占 폚, more preferably 170 ° C to 200 ° C), and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

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

In the production of the printed wiring board, the step of (III) piercing the insulating layer, (IV) the step of roughening the insulating layer, and the step of forming the conductor layer (V) may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. When the support is removed after the step (II), the removal of the support may be carried out between the steps (II) and (III), between the steps (III) and (IV), or between the steps ).

The step (III) is a step of perforating 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 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 in accordance with the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The procedure and condition of the roughening treatment are not particularly limited, and a known procedure and condition commonly used in forming the insulating layer of the printed wiring board can be adopted. For example, the swelling treatment with a swelling liquid, the coarsening treatment with an oxidizing agent, and the neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer. The swelling liquid is not particularly limited, but an alkaline solution, a surfactant solution and the like can be mentioned, and an alkaline solution is preferable, and a sodium hydroxide solution and a potassium hydroxide solution are more preferable as the alkaline solution. Examples of commercially available swelling liquids include "Swelling Dip Sicurgisan P", "Swelling Dip Sicurgisan SBU" manufactured by Atotech Japan Co., Ltd., and the like. The swelling treatment by the swelling liquid is not particularly limited, and can be performed, for example, by immersing the swelling liquid at 30 캜 to 90 캜 for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 占 폚 to 80 占 폚 for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include alkaline permanganic acid solutions 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 permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated at 60 캜 to 80 캜 for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercial oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., and "Dozing Solution / Securigans P". As the neutralization solution, an acidic aqueous solution is preferable. Commercially available products include, for example, &quot; Reduction Solution ㆍ Securigans P &quot; manufactured by Atotech Japan Co., The treatment with the neutralizing liquid can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes. From the standpoint of workability and the like, it is preferable to immerse the object subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 to 70 캜 for 5 to 20 minutes.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less, 250 nm or less, 200 nm or less, Or 100 nm or less. The arithmetic average roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. A specific example of the non-contact type surface roughness meter is "WYKO NT3300" manufactured by Vico Instruments.

Step (V) is a step of forming a conductor layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium do. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy and copper- ). &Lt; / RTI &gt; Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy And an alloy layer of 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, Is more preferable.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, the conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-custom method or a pull-to-body method. Hereinafter, examples in which the conductor layer is formed by the semi-specific method will be described.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

[Semiconductor device]

The semiconductor device of the present invention is characterized by including the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured by using the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices provided in electronic products (such as a computer, a mobile phone, a digital camera, a TV, and the like) and a vehicle (e.g., a motorcycle, a car, a tank, .

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

The method of mounting the semiconductor chip at the time of manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip effectively functions. Specifically, the method of wire bonding, flip chip mounting, A mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF), and the like. Here, the "mounting method using the bumpless buildup layer (BBUL)" refers to a "mounting method in which the semiconductor chip is directly buried in the concave portion of the printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board.

[Example]

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples. In the following description, &quot; part &quot; and &quot;% &quot; mean &quot; part by mass &quot; and &quot;% by mass &quot;, respectively, unless otherwise specified.

First, various measurement methods and evaluation methods will be described.

<Measurement of Minimum Melting Viscosity>

The melt viscosities of the resin composition layers in the adhesive films produced in Examples and Comparative Examples were measured. A parallel plate having a resin amount of 1 g and a diameter of 18 mm was used, and the temperature was changed from a start temperature of 60 ° C to 200 ° C, a temperature rise rate of 5 And the melt viscosity was measured under the measurement conditions of a temperature of 25 DEG C / minute, a measurement temperature interval of 2.5 DEG C, and a vibration of 1 Hz / deg.

<Measurement of breaking point elongation>

The adhesive films prepared in Examples and Comparative Examples were heated at 200 占 폚 for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as &quot; cured product for evaluation &quot;. The tensile elongation at break of the cured product for evaluation was measured in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.).

&Lt; Measurement of glass transition point >

The cured product for evaluation was cut into test pieces each having a width of about 5 mm and a length of about 15 mm and subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer ("Thermo Plus TMA8130" manufactured by Rigaku Corporation) . Specifically, after the test piece was mounted on the thermomechanical analyzer, the test piece was measured twice in succession under the measurement conditions of a load of 1 g and a temperature raising rate of 5 캜 / minute. In the second measurement, the glass transition point (Tg; 占 폚) was calculated.

&Lt; Measurement of dielectric loss tangent &

The cured product for evaluation was cut into test pieces having a width of about 2 mm and a length of 80 mm. The dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 占 폚 by a resonance perturbation method using a dielectric constant measuring device (HP8362B manufactured by Agilent Technologies). The two specimens were measured and the average value was calculated.

&Lt; Example 1 >

, 30 parts of a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 180) and 30 parts of a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., 55 parts of naphtha were dissolved with heating while stirring, and then cooled to room temperature. To this mixed solution, spherical silica (average particle diameter 0.5 mu m, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with an amino silane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., And the resulting mixture was kneaded with three rolls and uniformly dispersed. 40 parts of an active ester compound (&quot; HPC-8000-65T &quot;, active group equivalent approximately 223, and a toluene solution of a nonvolatile component of 65 mass%) 40 parts of an active ester compound (phenol resin , 20 parts of methyl ethyl ketone (hereinafter abbreviated as &quot; MEK &quot;) and cyclohexanone in a solid content of 30% by mass, manufactured by Tokyo Kasei Kogyo Co., , 4,5-triphenylimidazole ", 24 parts of a solid content of 2.5% by mass of MEK and cyclohexanone in a 1: 1 solution) and 10 parts of MEK were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish .

A PET film ("AL5" manufactured by LINTEC CO., LTD., Thickness: 38 mu m) having an alkyd resin-based release layer was prepared as a support. Resin varnish was applied uniformly on the release layer of the support to give a thickness of the dried resin composition layer of 40 占 퐉 and dried at 80 to 120 占 폚 (average 100 占 폚) for 5 minutes to prepare an adhesive film.

&Lt; Example 2 >

In Example 1, 14 parts of a triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%) was added to the roll dispersion , A resin varnish and an adhesive film were prepared in the same manner as in Example 1. [

&Lt; Example 3 >

In Example 2, 30 parts of a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 269) was mixed with a naphthol type epoxy resin ("ESN475V" manufactured by Shinnets Tetsu Sumikin Kagaku Co., 332) was changed to 30 parts, a resin varnish and an adhesive film were produced in the same manner as in Example 2.

<Example 4>

In Example 2, 30 parts of a biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: 269) was added to 100 parts by weight of a bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, ) Was changed to 30 parts, a resin varnish and an adhesive film were produced in the same manner as in Example 2. [

&Lt; Example 5 >

In the same manner as in Example 2 except that 3 parts of methacrylbutadiene styrene rubber particles ("EXL-2655" manufactured by Dow Chemical K.K.) were further added to the mixed solution in Example 2, resin varnish, A film was produced.

&Lt; Comparative Example 1 &

In Example 1, 24 parts of a curing accelerator ("2,4,5-triphenylimidazole" manufactured by Tokyo Kasei Kogyo Co., Ltd., a 1: 1 solution of MEK and cyclohexanone in a solid content of 2.5% by mass) Except that 6 parts of an accelerator ("1B2PZ" manufactured by Shikoku Chemicals Corporation, 1-benzyl-2-phenylimidazole, 10% by mass of solid content MEK solution) was used instead of the resin varnish Respectively.

&Lt; Comparative Example 2 &

In Example 1, 24 parts of a curing accelerator ("2,4,5-triphenylimidazole" manufactured by Tokyo Kasei Kogyo Co., Ltd., a 1: 1 solution of MEK and cyclohexanone in a solid content of 2.5% by mass) And 6 parts of an accelerator (&quot; DMAP &quot;, 4-dimethylaminopyridine, 5 mass% of solid solution of MEK) was used in place of the solvent used in Example 1 to prepare a resin varnish and an adhesive film.

&Lt; Comparative Example 3 &

40 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent approximately 223, and a toluene solution of a nonvolatile component of 65% by mass) in Example 1 was mixed with 40 parts of a phenol novolak-type polyfunctional cyanate ester resin (PT30, manufactured by RONJANJAN CO., LTD., Cyanate equivalent 124) was changed to 26 parts, and a resin varnish and an adhesive film were prepared in the same manner as in Example 1.

Claims (13)

(A) an epoxy resin, (B) an active ester compound, and (C) triphenylimidazole which may have a substituent. The resin composition according to claim 1, wherein the content of the component (B) is 1% by mass to 30% by mass based on 100% by mass of the nonvolatile component in the resin composition. The resin composition according to claim 1, wherein the content of the component (C) is 0.01% by mass to 5% by mass based on 100% by mass of the nonvolatile component in the resin composition. The resin composition according to claim 1, which comprises (D) an inorganic filler. The resin composition according to claim 4, wherein the content of the component (D) is 50% by mass or more based on 100% by mass of the nonvolatile component in the resin composition. 5. The resin composition according to claim 4, wherein the component (D) has an average particle diameter of 0.01 mu m to 3 mu m. The resin composition according to claim 4, wherein the component (D) is silica. The resin composition according to claim 1, which comprises (E) a thermoplastic resin. An adhesive film comprising a support and a resin composition layer comprising the resin composition according to claim 1 formed on the support. The adhesive film according to claim 9, wherein the lowest melt viscosity of the resin composition layer is 3000 poise or less. The adhesive film according to claim 9 or 10, wherein the cured resin composition layer has a breaking point elongation of 1.5% or more. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device comprising the printed wiring board according to claim 12.