KR101489175B1 - Resin composition - Google Patents

Abstract

A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the inorganic filler is surface-treated with a specific organic compound. The resin composition can form a plated conductor layer having a small arithmetic mean roughness and a root mean square roughness of the surface of the insulating layer and a sufficient fill strength in the wet roughening step, and also has PCT resistance.

Description

Resin composition {RESIN COMPOSITION}

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

2. Description of the Related Art In recent years, miniaturization and high performance of electronic devices have progressed, and in a multilayer printed wiring board, buildup layers are layered, and miniaturization and high density of wirings are required.

Various attempts have been made to this. For example, Patent Document 1 discloses a resin composition containing a silicon alkoxy oligomer. It is described that the insulating material formed by these compositions can have adhesiveness. Also, in Patent Documents 2 to 4, general formulation studies are also conducted. However, the performance was not necessarily satisfactory.

Japanese Patent Application Laid-Open No. 2006-117826 Japanese Patent Publication No. 4674730 Japanese Patent Publication No. 4686750 Japanese Patent Publication No. 4782870

A problem to be solved by the invention is to provide a plating conductor layer having a small arithmetic mean roughness and a root mean square roughness of a surface of an insulating layer and a sufficient fill strength in a wet roughening step, Cooker Test) resistance.

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the inorganic filler is surface- The present invention has been completed.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the inorganic filler is surface-treated with an organic compound having a hydroxyl group and a reactive group, Wherein the resin composition is a resin composition.

[2] The organic electroluminescent device described in [1], wherein the reactive group of the organic compound is at least one selected from the group consisting of amino group, epoxy group, mercapto group, methacryl group, acrylic group, vinyl group, Resin composition.

[3] The organic electroluminescence device described in [1] above, wherein the organic compound is selected from the group consisting of a compound of the following formula 1, a compound of the following formula 2, a compound of the following formula 3, an imidazole compound and an imidazole- Or more.

In the above Chemical Formulas 1 to 3,

R1 and R2 each independently represent a phenyl group, a benzyl group, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

R3 is an alkylene group having 1 to 5 carbon atoms or a phenylene group,

R4 is an alkylene group or a phenylene group having 1 to 5 carbon atoms,

R5 is an organic group having a hydroxy group,

R6 is a hydrogen atom, a methyl group, a carboxyl group or a phenyl group.

[4] The resin composition according to any one of [1] to [3], wherein the organic compound is 0.05 to 2% by mass when the inorganic filler (C) is 100% by mass.

[5] The method according to any one of [1] to [4], wherein after the inorganic filler is surface-treated with the organic compound, the silane coupling agent, alkoxysilane, alkoxy oligomer, aluminum- A coupling agent, and a zirconium-based coupling agent.

[6] The resin composition according to any one of [1] to [5], wherein the amount of carbon bonded to the surface of the inorganic filler (C) is 0.05 to 1.00 mg / m 2.

[7] The method according to any one of [1] to [6], wherein the resin composition is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength of the conductor layer and the insulating layer, Wherein the resin composition is cured to form an insulating layer and an arithmetic average roughness after roughening the surface of the insulating layer is 10 to 300 nm and a root mean square roughness of the root mean square is 10 to 480 nm Wherein the resin composition is a resin composition.

[8] A sheet-like laminated material characterized by containing the resin composition according to any one of [1] to [7].

[9] A multilayer printed wiring board in which an insulating layer is formed by a cured product of the resin composition according to any one of [1] to [7].

[10] A semiconductor device characterized by using the multilayered printed circuit board according to [9].

(EN) A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the inorganic filler is surface - treated with a specific organic compound, It is possible to form a plated conductor layer having a small arithmetic mean roughness and a root mean square root roughness of the insulating layer surface and a sufficient fill strength, and to provide a resin composition having PCT resistance.

The present invention provides a resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the inorganic filler has an organic compound having a hydroxyl group and a reactive group, And the like.

≪ (A) Epoxy resin >

Examples of the epoxy resin used in the present invention include, but not limited to, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, phenol novolak epoxy resin, tert- Naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy An epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spirocyclic epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin, and a halogenated epoxy resin. These may be used singly or in combination of two or more.

Among them, bisphenol A epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, naphthylene ether epoxy resin, anthracene type epoxy resin, and the like are preferable from the viewpoints of improvement of heat resistance, improvement of insulation reliability, An epoxy resin having a butadiene structure is preferable. Specifically, for example, bisphenol A type epoxy resin ("Epikote 828EL", "YL980" manufactured by Mitsubishi Chemical Corp.), bisphenol F type epoxy resin ("jER806H" manufactured by Mitsubishi Kagaku Co., HP4000D "," HP4032SS ", and" EXA4032SS "manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (" HP4700 "manufactured by DIC Corporation)," Epoxy resin having a butadiene structure (" PB-3600 " manufactured by Daicel Chemical Industries, Ltd.) having a biphenyl structure, NC3000H, NC3000L, NC3100, YX4000, YX4000H, YX4000HK, and YL6121 manufactured by Mitsubishi Chemical Corporation) (Mitsubishi EXA-7311 ", " EXA-7311L ", " EXA7311-G3 ", manufactured by DIC Corporation) have.

The epoxy resin may be used in combination of two or more kinds, but preferably contains an epoxy resin having two or more epoxy groups in one molecule. Among them, an aromatic epoxy resin (hereinafter referred to as " liquid epoxy resin ") which has two or more epoxy groups in one molecule and is liquid at a temperature of 20 캜 and three or more epoxy groups in one molecule, (Hereinafter referred to as " solid-state epoxy resin "), which is a solid phase, is more preferable. The term "aromatic epoxy resin" in the present invention means an epoxy resin having an aromatic ring structure in its molecule. When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, it is preferable that the resin composition has appropriate flexibility when the resin composition is used in the form of an adhesive film or that the cured product of the resin composition has an appropriate breaking strength, Is preferably in the range of 1: 0.1 to 1: 2, more preferably in the range of 1: 0.3 to 1: 1.8, more preferably in the range of 1: 0.6 to 1: 1.5, More preferable.

As the liquid epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, or a naphthalene type epoxy resin is preferable, and a naphthalene type epoxy resin is more preferable. These may be used singly or in combination of two or more.

Examples of the solid epoxy resin include tetrafunctional naphthalene type epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins Resins are preferable, and tetrafunctional naphthalene type epoxy resins, biphenyl type epoxy resins, or naphthylene ether type epoxy resins are more preferable. These may be used singly or in combination of two or more.

From the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition in the resin composition of the present invention, when the nonvolatile component in the resin composition is 100 mass%, the content of the epoxy resin is preferably 3 to 40 mass% , More preferably from 5 to 35 mass%, further preferably from 10 to 30 mass%.

<(B) Hardener>

Examples of the curing agent to be used in the present invention include, but are not limited to, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent and an acid anhydride curing agent, A curing agent, a naphthol-based curing agent and an active ester-based curing agent are preferable. These may be used singly or in combination of two or more.

Examples of the phenol-based curing agent and naphthol-based curing agent include, but are not limited to, phenol-based curing agents having a novolac structure and naphthol-based curing agents having a novolac structure, and phenol novolac resins, phenazine novolac resins containing a triazine skeleton, A naphthol novolak resin, a naphthol aralkyl type resin, a triazine skeleton-containing naphthol resin, and a biphenylaralkyl type phenol resin are preferable. Examples of commercially available products include biphenylaralkyl type phenol resins such as "MEH-7700", "MEH-7810", "MEH-7851", "MEH7851-4H" (manufactured by Meiwa Kasei Kogyo Co., SN170 "," SN180 ", and" SN190 "as the naphthol aralkyl type resin (" Nippon Kayaku K.K. ") as the naphthol novolac resin," NHN " , SN475, SN485, SN495, SN395, SN375 (manufactured by Toto Chemical), "TD2090" (manufactured by DIC Corporation) as phenol novolak resin, triazine skeleton LA3018 "," LA7052 "," LA7054 ", and" LA1356 "(manufactured by DIC Corporation), and the like. These may be used singly or in combination of two or more.

The active ester-based curing agent is not particularly limited, but generally includes ester groups having high reactivity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, Are preferably used. It is preferable that the active ester-based curing agent is obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- , p-cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri Hydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, and the like. One kind or two or more kinds of active ester type curing agents may be used. As the active ester type curing agent, the active ester type curing agent disclosed in Japanese Patent Application Laid-Open No. 2004-277460 may be used, or a commercially available active ester type curing agent may be used. As commercially available active ester-based curing agents, those containing a dicyclopentadienyldiphenol structure, acetylated phenol novolak, and benzoylated phenol novolac are preferred, and among them, a dicyclopentadienyldiphenol structure . Specifically, EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC Corporation, active equivalent weight about 223) containing dicyclopentadienyldiphenol structure and DC808 YLH1026 (manufactured by Mitsubishi Kagaku KK, having an activating group equivalent of about 200), YLH1030 (manufactured by Mitsubishi Chemical Corp., an activating group equivalent of about 149), phenol novolac benzoylate 201), YLH1048 (manufactured by Mitsubishi Chemical Corporation, having an active equivalent weight of about 245), and among these, HPC-8000-65T is preferable from the viewpoints of storage stability of the varnish and thermal expansion coefficient of the cured product.

As the active ester-based curing agent containing a dicyclopentadienyldiphenol structure, more specifically, a compound represented by the following general formula (4) may be mentioned.

In Formula 4,

R is a phenyl group or a naphthyl group,

k is 0 or 1,

n is an average of the repeating units of 0.05 to 2.5.

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

The benzoxazine-based curing agent is not particularly limited, and specific examples thereof include F-a, P-d (manufactured by Shikoku Chemicals Inc.), HFB2006M (manufactured by Shawako Co., Ltd.) and the like.

Examples of the cyanate ester curing agent include, but are not limited to, novolac (phenol novolac type, alkylphenol novolak type, etc.) cyanate ester type curing agent, dicyclopentadiene type cyanate ester type curing agent, bisphenol type Bisphenol F, bisphenol S, etc.) cyanate ester curing agents, and partially triarylated prepolymers thereof. The weight-average molecular weight of the cyanate ester-based curing agent is not particularly limited, but is preferably 500 to 4500, more preferably 600 to 3000. Specific examples of cyanate ester curing agents include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins derived from phenol novolak, cresol novolac, dicyclopentadiene structure-containing phenol resin, etc., and the like, such as bis (cyanate phenyl) thioether and bis , A partially triarylated prepolymer of these cyanate resins, etc. These may be used singly or in combination of two or more kinds. Examples of commercially available cyanate ester resins include phenol novolak type polyfunctional cyanate ester resins represented by the following formula (PT30, cyanate equivalent 124, manufactured by Lonza Japan K.K.), bisphenol (BA230, cyanate equivalent 232, manufactured by Lonza Japan K.K.), a dicyclopentadiene structure-containing cyanate ester resin represented by the following general formula (7) DT-4000, DT-7000, manufactured by Japan Kogyo Co., Ltd.).

In Formula 5,

n is an arbitrary number (preferably 0 to 20) as an average value.

In Formula 7,

n is a number from 0 to 5 as an average value.

Examples of the acid anhydride-based curing agent include, but are not limited to, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride , Anhydrous pyromellitic acid, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ , Ethylene glycol bis (anhydrotrimellitate), &lt; RTI ID = 0.0 &gt; And polymeric acid anhydrides such as styrene-maleic acid resin in which tylene and maleic acid are copolymerized.

From the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition in the resin composition of the present invention, the ratio of (A) the total number of epoxy groups of the epoxy resin to the total number of the reactors of the curing agent (B) To 1: 2, more preferably from 1: 0.3 to 1: 1.5, further preferably from 1: 0.4 to 1: 1. The total number of epoxy groups in the epoxy resin present in the resin composition, the value obtained by dividing the solid content of each epoxy resin by the epoxy equivalent, and the total number of reactors of the curing agent, the solid content of each curing agent, The value obtained by dividing by the equivalent of the reactor is the sum of all the curing agents.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100 mass%, the content of the curing agent is preferably 3 to 30 mass% , More preferably from 5 to 25 mass%, further preferably from 7 to 20 mass%.

<(C) Inorganic filler>

The inorganic filler (C) used in the present invention is not particularly limited, and examples thereof include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, Boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable. Further, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, or hollow silica is preferable, and fused silica is more preferable. Further, it is preferably spherical as silica. These may be used singly or in combination of two or more. As commercially available spherical fused silica, "SOC2" and "SOC1" manufactured by Adomex Co., Ltd. may be mentioned.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 占 퐉 or less, more preferably 3 占 퐉 or less, further preferably 1 占 퐉 or less, and more preferably 0.7 占 퐉 More preferably 0.5 μm or less, particularly preferably 0.4 μm or less, and particularly preferably 0.3 μm or less. On the other hand, in the case where the epoxy resin composition is a resin varnish, the average particle diameter of the inorganic filler is preferably 0.01 탆 or more, more preferably 0.03 탆 or more from the viewpoint of increasing the viscosity of the varnish and preventing the handling property from being lowered More preferably 0.05 mu m or more, and even more preferably 0.07 mu m or more. And particularly preferably at least 0.1 mu m. The average particle diameter 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 particle size distribution measuring apparatus, and the median diameter is determined as an 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 particle size distribution measuring apparatus, LA-500, 750, 950 manufactured by Horiba Seisakusho Co., Ltd. can be used.

When the inorganic filler is blended, the content is preferably 20% by mass or more, more preferably 30% by mass or more, from the viewpoint of lowering the thermal expansion coefficient of the cured product when the nonvolatile component in the resin composition is 100% By mass, more preferably not less than 40% by mass, and still more preferably not less than 50% by mass. From the viewpoint of improving the mechanical properties of the cured product, the content is preferably 85% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, further preferably 70% by mass or less.

The inorganic filler (C) can be prepared by surface-treating with a silazane compound in advance from the viewpoints of improvement in dispersibility of resin varnish, reduction in arithmetic average roughness, and reduction in root mean square root roughness. Surface treatment with an organic compound having a hydroxyl group and a reactive group and a boiling point of 100 ° C or higher after surface treatment with a silazane compound is advantageous in terms of improvement in dispersibility and improvement in affinity with a conductor layer. Examples of the silazane compound include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa (t-butyl) , Hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilane 1,3-dimethyl tetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-di Propyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilazane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclohexane And trisilazane. Of these, hexamethyldisilazane is particularly preferable. These may be used singly or in combination of two or more. As the spherical fused silica surface-treated with hexamethyldisilazane, "SC2050-SQ" manufactured by Adomex Co., Ltd. may be mentioned.

The organic compound having a hydroxyl group and a reactive group and having a boiling point of 100 ° C or higher used in the present invention is covalently bonded to an inorganic filler by means of a covalent bond with the inorganic filler so that sufficient coverage is possible and the reactive group improves the dispersibility in the resin composition. Further, the boiling point is 100 占 폚 or higher, whereby the surface treatment of the organic compound can be performed stably while evaporating water generated by dehydration condensation. The upper limit value of the boiling point is preferably 500 占 폚, more preferably 400 占 폚, and still more preferably 300 占 폚. In the present invention, the &quot; boiling point &quot; of an organic compound means a boiling point under a standard atmospheric pressure (0.101325 MPa). The organic compound is not particularly limited, but the reactive group of the organic compound is preferably at least one selected from an amino group, an epoxy group, a mercapto group, a methacryl group, an acrylic group, a vinyl group and a ureido group, More preferable. The organic compound preferably contains substantially no element selected from the group consisting of silicon, aluminum, titanium, and zirconium. Here, the term "substantially not contained" means that the element does not contain an element selected from the group consisting of silicon, aluminum, titanium, and zirconium, except when it is contained as an inevitable impurity. The organic compound is more preferably at least one compound selected from the group consisting of compounds represented by the following general formulas (1), (2), (3), imidazole compounds and imidazole-epoxy adducts

Formula 1

In Formula 1,

R1 and R2 each independently represent a phenyl group, a benzyl group, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,

R3 is an alkylene group having 1 to 5 carbon atoms or a phenylene group.

R1 and R2 are preferably a phenyl group, a benzyl group or a hydrogen atom. R3 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms.

(2)

In Formula 2,

R4 is an alkylene group having 1 to 5 carbon atoms or a phenylene group.

R4 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms.

(3)

In Formula 3,

R5 is an organic group having a hydroxy group,

R6 is a hydrogen atom, a methyl group, a carboxyl group or a phenyl group.

R5 is preferably a monovalent organic group having a hydroxyl group and an amino group, and more preferably a monovalent organic group represented by the following formula (8). R6 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

In Formula 8,

R7 and R8 each independently represent a hydroxyl group, a phenol group, a hydroxymethyl group, or a hydroxyethyl group,

n is an arbitrary integer of 0 to 5,

The * part of the above formula bonds to the N atom.

R7 and R8 are each independently preferably a hydroxymethyl group or a hydroxyethyl group, more preferably a hydroxyethyl group. n is preferably 1 to 3.

Further, a compound represented by the following general formula (9) may also be used.

More specifically, there may be mentioned N-benzylaminoethanol, N-anilinoethanol, glycidol, imidazole-epoxy adduct, benzotriazole derivative, 3-benzylamino-1-propanol, 2-ethylaminoethanol, 2-propylaminoethanol, 2-isopropylaminoethanol, 2-butylaminoethanol, 2 - ((1-methylpropylamino) Phenylamino-1-butanol, 5-phenylamino-1-pentanol and 1- (2-aminoethyl) -Hydroxyethyl) imidazole is still more preferable. Among them, from the viewpoints of handling safety, imparting high adhesion with a conductive layer, and improving storage stability, it is preferable to use N-benzylaminoethanol, N-anilinoethanol, glycidol, 2,2 - [{ 1-yl) methyl} imino] bisethanol, 1- (2-hydroxyethyl) imidazole and imidazole-epoxy adduct are particularly preferable.

(C) A method of surface-treating an inorganic filler with the organic compound is a method of adding (C) an inorganic filler to a rotary mixer, spraying the organic compound, and (C) stirring the inorganic filler for 5 to 30 minutes .

The content of the organic compound is preferably not more than 2% by mass, more preferably not more than 1.8% by mass, more preferably not more than 1.6% by mass, based on 100% by mass of the inorganic filler (C) from the viewpoint of preventing an increase in melt viscosity. Or less, more preferably 1.4 mass% or less. From the viewpoints of improving the dispersibility of the resin varnish and improving the covering ratio of the inorganic filler, the amount is preferably 0.05 mass% or more, more preferably 0.1 mass% or more, more preferably 0.15 mass% or more, and 0.2 mass% Still more preferable.

(C) a silane coupling agent, an alkoxysilane, an alkoxy oligomer, an aluminum-based coupling agent, a silane coupling agent, a silane coupling agent, or a silane coupling agent, from the viewpoints of improving the hydrophobicity of the inorganic filler after surface treatment with the organic compound and further improving the dispersibility by reacting with an unreacted silanol group , A titanium-based coupling agent, and a zirconium-based coupling agent.

As the silane coupling agent, an epoxy silane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, or the like can be used. These may be used singly or in combination of two or more. Specifically, there may be mentioned, for example, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclo Aminopropyltrimethoxysilane, N-2 (aminoethyl) aminopropyltrimethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, Aminosilane coupling agents such as trimethoxy silane, and mercaptosilane coupling agents such as mercaptopropyl trimethoxy silane and mercaptopropyl triethoxy silane.

As the alkoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolylsilane, triazinilane and the like can be used. These may be used singly or in combination of two or more.

The alkoxy oligomer refers to a low molecular weight resin having an organic group and an alkoxysilyl group together and includes, for example, a methyl group-containing alkoxy oligomer, a phenyl group-containing alkoxy oligomer, a methyl / phenyl group-containing alkoxy oligomer, an epoxy group-containing alkoxy oligomer, Alkoxy oligomers, acrylic group-containing alkoxy oligomers, methacryl group-containing alkoxy oligomers, ureido group-containing alkoxy oligomers, isocyanate group-containing alkoxy oligomers, vinyl group-containing alkoxy oligomers and the like. These may be used singly or in combination of two or more.

Examples of the aluminum-based coupling agent include aluminum isopropylate, mono sec-butoxyaluminum diisopropylate, aluminum sec-butylate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris Acetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate, cyclic aluminum oxide isopropylate, cyclic aluminum oxide stearate , Cyclic aluminum oxide octylate, cyclic aluminum oxide stearate, and the like. These may be used singly or in combination of two or more.

Examples of the titanium-based coupling agent include butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolamine), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) (Dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2- Ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) Tridecyl) phosphite titanate, isopropyltri octanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl diisostearoylidene Isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris , Isopropyltri (N-amidoethylaminoethyl) titanate, and the like. These may be used singly or in combination of two or more.

Examples of the zirconium-based coupling agent include zirconium IV (2,2-bis (2-propanolate methyl) butanolate, trisneodecanolate, zirconium IV (2,2- Methyl) butanolate, tris (dodecylbenzyl sulfonate)), zirconium IV (2,2-bis (2-propanolate methyl) butanolate, tris (dioctyl) phosphate), zirconium IV Bis (2-propenolate methyl) butanolate, tris 2-methyl 2-propenolate), zirconium IV-bis (2,2- Benzoate), zirconium IV (2,2-bis (2-propanolate methyl) butanolate, tris (diisooctyl) pyrophosphate), zirconium IV (2,2- Butanolate, tris (2-propenoate), zirconium IV (2,2-bis (2-propanolate methyl) ), Zirconium IV, 2,2-bis (2-propanolate methyl) butanolate, bis (3-mercaptopropanoate) Methyl) butanolate and tris (2-amino) phenylate), zirconium IV (2,2-bis (2-propanolate methyl) butanolate, tris (diisooctyl) pyrophosphate) (2-ethyl-2-propenolate methyl) -1,3-propenedioate, cyclodiimide 2,2- (bis-2-propanolate methyl) butanolate, pyro Phosphate), zirconium IV (tetrakis-2,2- (bis-2-propanolate methyl) butanolate, ditridecylhydrogenphosphite 2-mol adduct, etc. These may be one or two kinds These may be used in combination.

(C) The amount of carbon per unit area bonded to the surface of the inorganic filler after the surface treatment of the inorganic filler is preferably 1.00 mg / m 2 or less, more preferably 0.75 mg / m 2 or less, still more preferably 0.70 mg / , More preferably 0.65 mg / m 2 or less, particularly preferably 0.60 mg / m 2 or less, particularly preferably 0.55 mg / m 2 or less, and particularly preferably 0.50 mg / m 2 or less. On the other hand, the amount of carbon per unit area bonded to the surface is preferably 0.05 mg / m 2 or more, more preferably 0.08 mg / m 2 or more, more preferably 0.11 mg / m 2 or more, and more preferably 0.14 mg / More preferably 0.17 mg / m 2 or more, particularly preferably 0.20 mg / m 2 or more, particularly preferably 0.23 mg / m 2 or more, further preferably 0.26 mg / m 2 or more. As a result, the arithmetic mean roughness and the root mean square root roughness after the wet roughening step are stabilized, and the conductor layer with high fill strength can be stably formed.

The degree of the surface treatment of the inorganic filler is determined by the amount of carbon per unit surface area of the inorganic filler after the surface treatment (for example, methyl ethyl ketone (MEK)), The amount of carbon per unit area bonded) can be quantified. For example, the amount of carbon per unit area bonded to the surface of the inorganic filler can be calculated by the following procedure. A sufficient amount of MEK as a solvent is added to the inorganic filler after the surface treatment, followed by ultrasonic cleaning. After the supernatant is removed and the solid content is dried, the amount of carbon bonded to the surface of the inorganic filler is measured using a carbon analyzer. By dividing the obtained amount of carbon by the specific surface area of the inorganic filler, the amount of carbon per unit area bonded to the inorganic filler is calculated.

On the other hand, as the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

The peel strength of the conductor layer and the insulating layer obtained by curing the resin composition of the present invention to form an insulating layer, roughening the surface of the insulating layer, and plating, Of the present invention can be grasped by the measurement method described in &quot; Measurement of &quot;

The fill strength is preferably 0.8 kgf / cm or less, more preferably 0.9 kgf / cm or less, more preferably 1.0 kgf / cm or less, and even more preferably 1.5 kgf / cm or less. The peel strength is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more.

The arithmetic mean roughness (Ra value) and the root average square root roughness (Rq value) of the resin composition of the present invention after curing the insulating layer to form the insulating layer and roughening the surface of the insulating layer are determined by the arithmetic average roughness (Ra value), and the average square root roughness (Rq value) of the root mean square value &gt;.

The arithmetic mean roughness (Ra value) is preferably 300 nm or less, more preferably 260 nm or less, more preferably 240 nm or less, still more preferably 220 nm or less, and less than 200 nm in order to reduce transmission loss of the electric signal More preferably 170 nm or less, particularly preferably 160 nm or less, further preferably 150 nm or less. On the other hand, the arithmetic mean roughness (Ra value) is preferably 10 nm or more, more preferably 20 nm or more, further preferably 30 nm or more, further preferably 40 nm or more, and more preferably 50 nm or more, Particularly preferred.

The average square root roughness (Rq value) is preferably 480 nm or less, more preferably 440 nm or less, still more preferably 420 nm or less, still more preferably 380 nm or less, and 340 nm or less Still more preferably 300 nm or less, particularly preferably 260 nm or less, further preferably 220 nm or less. On the other hand, the root mean square roughness (Rq value) of the root mean square roughness is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, still more preferably 70 nm or more, Is particularly preferred.

<(D) Curing accelerator>

By containing the curing accelerator in addition to the resin composition of the present invention, the epoxy resin and the curing agent can be efficiently cured. The curing accelerator is not particularly limited, and examples thereof include amine curing accelerators, guanidine curing accelerators, imidazole curing accelerators, phosphonium curing accelerators, and metal curing accelerators. These may be used singly or in combination of two or more.

Examples of the amine-based curing accelerator include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) , 8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU), and the like. These may be used singly or in combination of two or more.

Examples of the guanidine curing accelerator include, but are not limited to, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, Phenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4. 0] deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and 1- (o-tolyl) biguanide. These may be used singly or in combination of two or more.

Examples of the imidazole-based curing accelerator include, but are not limited to, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- methylimidazole, 2-phenylimidazole, Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- Diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine Phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole isocyanuric acid adduct, Benzimidazolium chloride, 2-methylimidazoline, 2-methylimidazoline, 2-methylimidazoline, 2- Imidazole compounds such as phenylimidazoline, and adducts of imidazole compounds and epoxy resins. These may be used singly or in combination of two or more.

Examples of the phosphonium curing accelerator include, but are not limited to, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These may be used singly or in combination of two or more.

In the resin composition of the present invention, the content of the curing accelerator (excluding the metal-based curing accelerator) is preferably in the range of 0.005 to 1% by mass, more preferably 0.01 to 0.5% The range of mass% is more preferable. When the amount is less than 0.005 mass%, the curing tends to be slow and the thermosetting time tends to be long. When it exceeds 1 mass%, the storage stability of the resin composition tends to decrease.

The metal-based curing accelerator is not particularly limited, and examples thereof 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, zinc 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. Specific examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate and zinc stearate. These may be used singly or in combination of two or more.

In the resin composition of the present invention, the addition amount of the metal-based curing accelerator is preferably 25 to 500 ppm based on the metal-based curing catalyst when the nonvolatile component in the resin composition is 100 mass% More preferably 200 ppm. If it is less than 25 ppm, it tends to make it difficult to form a conductor layer having a low arithmetic average roughness with good adhesion to the surface of the insulating layer. When it exceeds 500 ppm, the storage stability and insulating properties of the resin composition tend to be lowered.

&Lt; (E) Thermoplastic resin >

The resin composition of the present invention can further improve the mechanical strength of the cured product by containing the (E) thermoplastic resin and improve the film formability when it is used in the form of an adhesive film. Examples of such a thermoplastic resin include phenoxy resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone Resins, and polyester resins. These thermoplastic resins may be used alone or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000 in view of improvement in film formability, mechanical strength, and improvement in compatibility of the resin varnish. The weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the weight average molecular weight by the GPC method was measured by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring apparatus and Shodex K-800P / K-804L manufactured by Showa Denko K.K. / K-804L can be measured using a calibration curve of standard polystyrene at a column temperature of 40 占 폚 using chloroform or the like as the mobile phase.

When the (E) thermoplastic resin is blended in the resin composition of the present invention, the content of the thermoplastic resin in the resin composition is not particularly limited, but it is preferably 0.1 to 10% by mass based on 100% By mass, more preferably from 1 to 5% by mass. If the content of the thermoplastic resin is too small, the effect of improving the film formability and mechanical strength tends not to be exhibited. If the content is too large, the melt viscosity tends to increase and the arithmetic mean roughness of the surface of the insulating layer after the wet coarsening step tends to increase .

&Lt; (F) Rubber particles >

By containing (F) rubber particles in addition to the resin particles of the present invention, the plating film strength can be improved, and drilling workability, dielectric loss tangent and stress relaxation effect can be obtained. The rubber particles that can be used in the present invention are not soluble in an organic solvent used for preparing varnishes of the resin composition but are not compatible with hardeners or epoxy resins as essential components . Therefore, the rubber particles are present in a dispersed state in the varnish of the resin composition of the present invention. Generally, such rubber particles are prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in an organic solvent or a resin, thereby forming a granular phase.

Preferred examples of the rubber particles usable in the present invention include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles and the like. The core-shell-type rubber particle is a rubber particle having a core layer and a shell layer, for example, a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer and the core layer of the inner layer is composed of a rubber- A three-layer structure composed of a glassy polymer, an intermediate layer made of a rubbery polymer and a core layer made of a glassy polymer, and the like. The glassy polymer is composed of, for example, a polymer of methyl methacrylate and the like, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber). The rubber particles may be used in combination of two or more. Specific examples of the core-shell type rubber particles include stapylloid AC3832, AC3816N, IM-401 (revised) 1, IM-401 (revised) 7-17 (trade name, manufactured by Gansu Kasei Seisakusho), Metablen KW- 4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter 0.5 탆, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter 0.5 탆, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Metablen W300A (average particle diameter 0.1 mu m) and W450A (average particle diameter 0.2 mu m) (manufactured by Mitsubishi Rayon Co., Ltd.).

The average particle diameter of the rubber particles is preferably in the range of 0.005 to 1 占 퐉, and more preferably in the range of 0.2 to 0.6 占 퐉. The average particle diameter of the rubber particles used in the present invention can be measured by a dynamic light scattering method. For example, the rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber particles is measured using a concentrated system particle diameter analyzer (FPAR-1000, manufactured by Otsuka Denshi Co., Ltd.) Can be measured on the basis of mass and the median diameter can be measured as the average particle diameter.

The combined flow rate of the rubber particles is preferably from 1 to 10% by mass, more preferably from 2 to 5% by mass, based on 100% by mass of the nonvolatile component in the resin composition.

<(G) Flame Retardant>

The resin composition of the present invention can impart flame retardancy by further containing a flame retardant (G). Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicon-based flame retardant, a metal hydroxide, and the like. Specific examples of the organophosphorus flame retardant include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ and HCA-NQ manufactured by Sankyo Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Kogyo Co., TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, manufactured by Hokko Chemical Industries, Ltd., TPO , PPQ, OP930 manufactured by Clariant K.K. and PX200 manufactured by Daihachi Kagaku Co., Ltd., phosphorus-containing epoxy resins such as FX289, FX305 and TX0712 manufactured by Toto Chemical Co., Ltd., Phosphorus-containing phenoxy resins such as ERF001 manufactured by Kagaku Kogyo Co., Ltd., phosphorus-containing epoxy resins such as YL7613 manufactured by Japan Epoxy Resin Co., Ltd., and the like. Specific examples of the organic nitrogen-containing phosphorus compound include phosphoric acid ester amide compounds such as SP670 and SP703 manufactured by Shikoku Chemical Industry Co., Ltd., SPB100, SPE100 manufactured by Otsuka Chemical Co., Ltd., FP-series manufactured by FUSEMIZE YAKUSHO Co., And the like. Specific examples of the metal hydroxide include magnesium hydroxide such as UD65, UD650 and UD653 manufactured by Ube Industries, Ltd., B-30, B-325, B-315, B- 303, and UFH-20, and the like.

<Other ingredients>

In the resin composition of the present invention, other components may be blended as needed within a range not hindering the effect of the present invention. Examples of the other components include thermosetting resins such as vinylbenzyl compounds, acrylic compounds, maleimide compounds and block isocyanate compounds, organic fillers such as silicone powder, nylon powder and fluorine powder, thickeners such as allene and bentone, Based antifoaming agents or leveling agents, imidazole-based, thiazole-based, triazole-based and silane-based coupling agents, phthalocyanine blue, phthalocyanine green, iodine green, dithazol yellow, carbon black, etc. 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 solvent or the like is added, if necessary, and the mixture is mixed using a rotary mixer or the like.

The use of the resin composition of the present invention is not particularly limited, but the resin composition of the present invention can be suitably used for various applications such as a sheet-like laminate material such as an adhesive film and a prepreg, a circuit board (laminate board, multilayer printed wiring board, etc.), a solder resist, , A hole-filling resin, a component-embedded resin, and the like. Among them, in the production of a multilayer printed wiring board, it can be suitably used as a resin composition for forming an insulating layer, and can be more suitably used as a resin composition for forming a conductor layer by plating. The resin composition of the present invention may be applied to a circuit board in a varnish state to form an insulating layer, but industrially, it is generally preferable to use it in the form of a sheet-like laminated material such as an adhesive film or a prepreg. The softening point of the resin composition is preferably 40 to 150 DEG C from the viewpoint of the lamination property of the sheet-like laminated material.

&Lt; Adhesive film &

The adhesive film of the present invention can be produced by a method known to those skilled in the art, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, applying the resin varnish to a support using a die coater or the like, , Or drying the organic solvent by heating or hot air blowing to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve, Carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Two or more kinds of organic solvents may be used in combination.

The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. The amount of the organic solvent in the varnish, and the boiling point of the organic solvent. However, by drying the varnish containing, for example, 30 to 60 mass% of the organic solvent at 50 to 150 캜 for about 3 to 10 minutes, A layered adhesive film can be formed.

The thickness of the resin composition layer formed in the adhesive film is preferably not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 mu m, the resin composition layer preferably has a thickness of 10 to 100 mu m, more preferably 20 to 80 mu m.

Examples of the support include films of polyolefins such as polyethylene, polypropylene and polyvinyl chloride, films of polyester such as polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyethylene naphthalate, polycarbonate film, And various plastic films such as a film. In addition, a metal foil such as a mold release, a copper foil, and an aluminum foil may be used. The support and the protective film to be described later may be subjected to a surface treatment such as a mat treatment or a corona treatment. In addition, the releasing treatment may be carried out with a releasing agent such as a silicone resin-based releasing agent, an alkyd resin-based releasing agent, or a fluororesin-based releasing agent.

The thickness of the support is not particularly limited, but is preferably 10 to 150 mu m, more preferably 25 to 50 mu m.

On the surface of the resin composition layer on which the support is not closely adhered, a protective film corresponding to the support can be further laminated. The thickness of the protective film is not particularly limited, but is, for example, 1 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 may be rolled up and stored.

<Multilayer Printed Circuit Board Using Adhesive Film>

Next, an example of a method for producing a multilayered printed circuit board using the adhesive film produced as described above will be described.

First, the adhesive film is laminated on one side or both sides of the circuit board using a vacuum laminator. Examples of the substrate used for the circuit board include a glass epoxy resin, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the circuit board means a patterned conductor layer (circuit) formed on one side or both sides of the substrate. In the multilayered printed circuit board in which the conductor layer and the insulating layer are alternately laminated, the outermost layer of the multilayered printed circuit board may be a conductor layer (circuit) formed by patterning one or both sides of the outermost layer of the multilayered printed circuit board. do. Further, the surface of the conductor layer may be subjected to a harmonic treatment in advance by blackening treatment, copper etching, or the like.

In the laminate, if the adhesive film has a protective film, the protective film is removed, and if necessary, the adhesive film and the circuit board are preheated, and the adhesive film is pressed and heated on the circuit board while being pressed and heated. In the adhesive film of the present invention, a method of laminating a circuit substrate under reduced pressure by a vacuum laminating method is suitably used. The lamination conditions are not particularly limited. For example, the pressing temperature (lamination temperature) is preferably 70 to 140 占 폚, and the pressing pressure is preferably 1 to 11 kgf / cm 2 (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m &lt; 2 &gt;) and laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a continuous type in a roll. Vacuum laminates can be made using commercial vacuum laminators. As a commercially available vacuum laminator, for example, a vacuum applicator manufactured by Nichigo Morton K.K., a vacuum pressurized laminator manufactured by Takeda Chemical Industries, Ltd., a roll type dry coater manufactured by Hitachi Industries, Ltd., Hitachi Aichi Kogyo Co., Ltd. A vacuum laminator and the like.

Further, the lamination step for heating and pressurizing under reduced pressure can also be carried out using a general vacuum hot press machine. For example, it can be carried out by pressing a metal plate such as a heated SUS plate from the support layer side. Press conditions, the, of usually 1 × 10 ^-2 MPa or lower, preferably reduced pressure (減壓度) is downward pressure of less than 1 × 10 ^-3 MPa. The heating and pressurization can be carried out in one step, but it is preferable that the conditions are divided into two or more steps from the viewpoint of controlling the exudation of the resin. For example, the first-stage press is performed at a temperature of 70 to 150 DEG C, a pressure of 1 to 15 kgf / cm2, and a second-stage press at a temperature of 150 to 200 DEG C and a pressure of 1 to 40 kgf / . The time for each step is preferably 30 to 120 minutes. Examples of commercially available vacuum hot presses include MNPC-V-750-5-200 manufactured by Meikishesakusho Co., Ltd.) and VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.).

When an adhesive film is laminated on a circuit board and then cooled to a temperature near room temperature, when the support is peeled off, it is peeled and thermally cured to form an insulating layer on the circuit board. The conditions of the thermosetting may be appropriately selected depending on the type and content of the resin component in the resin composition, and preferably 20 to 180 minutes at 150 to 220 DEG C, more preferably 30 to 120 minutes at 160 to 210 DEG C .

After the formation of the insulating layer, if the support is not peeled off before curing, the peeling is carried out here. Then, if necessary, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. The drilling can be carried out by a known method such as drilling, laser, plasma or the like, or by a combination of these methods if necessary. However, if drilling with a laser such as a carbon dioxide gas laser or a YAG laser is the most drastic This is a common method.

Subsequently, a conductive layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the case of wet plating, the surface of the insulating layer is subjected to a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order to form an unevenness anchor. The swelling treatment with the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 캜 for 5 to 20 minutes. Examples of the swelling solution include an alkaline solution and a surfactant solution, and preferably an alkaline solution. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, manufactured by Atotech Japan Ltd., And the like. The roughening treatment with an oxidizing agent is carried out by immersing the insulating layer in an oxidizing agent solution at 60 to 80 占 폚 for 10 to 30 minutes. As the oxidizing agent, for example, an alkaline permanganic acid solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like can be given. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and Dozing Solution Cecrigant P manufactured by Atotech Japan K.K. The neutralization treatment by the neutralization liquid is carried out by immersing in the neutralization liquid at 30 to 50 캜 for 3 to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercial product, Reduction Soluble Leucine · Sucurentan P manufactured by Atotech Japan K.K.

Subsequently, a conductor layer is formed by combining electroless plating and electrolytic plating. It is also possible to form a plating resist having an inverse pattern to that of the conductor layer, and to form the conductor layer only by electroless plating. As a pattern formation method thereafter, for example, a subtractive method, a semi-specific method and the like known to those skilled in the art can be used.

<Prepreg>

The prepreg of the present invention can be produced by impregnating the sheet-like reinforcing base material with the resin composition of the present invention by a hot-melt method or a solvent method and heating and semi-curing the resin composition. That is, the resin composition of the present invention may be a prepreg impregnated with a sheet-like reinforcing base material. As the sheet-like reinforcing base material, for example, a fiber composed of fibers which are commonly used as prepreg fibers such as glass cloth or aramid fiber can be used.

The hot-melt method is a method in which a resin is temporarily coated on a coating material having good releasability from the resin without dissolving the resin in an organic solvent and laminated on the sheet-like reinforcing base material, or the resin is dissolved in an organic solvent, On a sheet-like reinforcing base material by means of an extruder or the like to form a prepreg. The solvent method is a method in which a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as an adhesive film, the sheet-like reinforcing base material is immersed in the varnish, the resin varnish is impregnated into the sheet- to be.

<Multilayer Printed Circuit Board Using Prepreg>

Next, an example of a method for producing a multilayered printed circuit board using the prepreg produced as described above will be described. One prepreg of the present invention or a plurality of prepregs according to the present invention is superimposed on a circuit board, sandwiched between metal plates with a release film interposed therebetween, and vacuum press laminated under pressure and heating conditions. The pressurization and heating conditions are preferably a pressure of 5 to 40 kgf / cm 2 (49 × 10 ⁴ to 392 × 10 ⁴ N / m 2) and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Further, similarly to the adhesive film, it is also possible to laminate the prepreg on the circuit board by the vacuum lamination method, followed by heating and curing. Thereafter, in the same manner as described above, the conductor layer is formed by plating after the surface of the cured prepreg is roughened to produce a multilayer printed wiring board.

<Semiconductor Device>

A semiconductor device can be manufactured by using the multilayered printed circuit board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion (conductive portion) of the multilayered printed circuit board of the present invention. The &quot; conduction site &quot; is a &quot; location for transmitting electrical signals in the multilayered printed circuit board &quot;, and may be a surface or a buried site. 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 when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip effectively functions. Specifically, the semiconductor chip mounting method, the flip chip mounting method, the bump- (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a nonconductive film (NCF).

Refers to a mounting method in which a semiconductor chip is directly buried in a concave portion of a multilayer printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board to each other. The BBUL method 1), and the BBUL method 2).

BBUL method 1) A mounting method for mounting a semiconductor chip on a concave portion of a multilayer printed wiring board using an underfill

BBUL method 2) A mounting method for mounting a semiconductor chip on a concave portion of a multilayer printed wiring board using an adhesive film or prepreg

The BBUL method 1) specifically includes the following steps.

Step 1) A conductor layer is removed from both sides of the multilayer printed wiring board, and through holes (through holes) are formed by a laser or a mechanical drill.

Step 2) An adhesive tape is attached to one surface of the multilayer printed wiring board, and the bottom surface of the semiconductor chip is arranged to be fixed on the adhesive tape in the through hole. The semiconductor chip at this time is preferably lower than the height of the through hole.

Step 3) An underfill is injected and filled in the gap between the through hole and the semiconductor chip, thereby fixing the semiconductor chip to the through hole.

Step 4) Thereafter, the adhesive tape is peeled to expose the bottom surface of the semiconductor chip.

Step 5) The adhesive film or the prepreg of the present invention is laminated on the bottom surface side of the semiconductor chip to cover the semiconductor chip.

Step 6) After curing the adhesive film or the prepreg, a hole is drilled by laser to expose the bonding pad on the bottom surface of the semiconductor chip, and the roughening treatment, the electroless plating, and the electrolytic plating are performed as described above, . If necessary, the adhesive film or the prepreg may be further laminated.

The BBUL method 2) specifically includes the following steps.

Step 1) A photoresist film is formed on the conductor layers on both surfaces of the multilayer printed wiring board, and an opening is formed only on one side of the photoresist film by a photolithography method.

Step 2) The conductor layer exposed in the opening is removed by an etching solution to expose the insulating layer, and then the resist film on both sides is removed.

Step 3) Using a laser or a drill, remove all of the exposed insulating layer and drill holes to form recesses. The energy of the laser is preferably a laser capable of adjusting the energy so as to lower the laser absorption rate of copper and increase the laser absorption rate of the insulating layer, and a carbon dioxide gas laser is more preferable. By using such a laser, it is possible to remove only the insulating layer without penetrating the conductor layer that is opposite to the opening portion of the conductor layer.

Step 4) The bottom surface of the semiconductor chip is disposed in the concave portion toward the opening side, and the adhesive film or the prepreg of the present invention is laminated from the opening side to cover the semiconductor chip and fill the gap between the semiconductor chip and the concave portion. The semiconductor chip at this time is preferably lower than the height of the concave portion.

Step 5) After the adhesive film or the prepreg is cured, a hole is drilled with a laser to expose the bonding pad on the bottom surface of the semiconductor chip.

Step 6) The roughening treatment, the electroless plating, and the electrolytic plating shown above are performed to connect the wirings and further laminate the adhesive film or the prepreg if necessary.

Among the semiconductor chip mounting methods, in view of miniaturization of the semiconductor device and reduction of the transmission loss, since the solder is not used, the thermal history is not applied to the semiconductor chip, and the twist of the solder and the resin can be generated in the future The BBUL method 1) and the BBUL method 2) are more preferable, and the BBUL method 2) is more preferable.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

 <Methods of measurement and evaluation>

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

<Preparation of samples for measurement of peel strength, arithmetic mean roughness (Ra value), and root mean square roughness (Rq value)

(1) Underlayer treatment of inner layer circuit board

(Thickness: 18 mu m, substrate thickness: 0.3 mm, R5715ES manufactured by Matsushita Electric Industrial Co., Ltd.) on which an inner layer circuit was formed was etched with a thickness of 1 mu m with CZ8100 manufactured by MEC Corp. to obtain a copper surface .

(2) Laminate of adhesive film

The adhesive films prepared in Examples and Comparative Examples were laminated on both surfaces of an inner layer circuit board using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meikisha Chemical Co., Ltd.). The laminate was subjected to pressure reduction for 30 seconds to set the air pressure to 13 hPa or less, and then press for 30 seconds at 100 占 폚 under a pressure of 0.74 MPa.

(3) Curing of resin composition

After the PET film was peeled from the laminated adhesive film, the resin composition was cured at 100 캜 for 30 minutes and further at 180 캜 for 30 minutes. In Example 10, the PET film was peeled off after thermosetting under the same conditions to form an insulating layer.

(4) Harmonization processing

The inner layer circuit board on which the insulating layer was formed was immersed in a Swelling dip · Sucrygant P (glycol ethers, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C as for 5 minutes, example 7 in 60 ℃ 10 minutes, and immersed in, and then to a roughening solution, Atotech Japan Concentrate in manufactured by right or wrong and compact _{P (KMnO 4: 60g / L} , NaOH: of 40g / L Aqueous solution) at 80 ° C for 15 minutes and for Example 10 at 80 ° C for 20 minutes. Finally, as a neutralizing solution, Reduction Solyl Leucine · Sucurentan P (glyoxal, sulfuric acid By weight) at 40 캜 for 5 minutes. After drying at 80 占 폚 for 30 minutes, the arithmetic mean roughness (Ra value) and the root mean square roughness (Rq value) of the surface of the insulating layer after the coarsening treatment were measured.

(5) Plating by semi-permanent method

To form a circuit on the surface of the insulating layer, the inner-layer circuit board was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. After an annealing treatment was performed by heating at 150 占 폚 for 30 minutes, an etching resist was formed, and a pattern was formed by etching, followed by copper sulfate electroplating to form a conductor layer with a thickness of 35 占 퐉. Next, annealing was performed at 200 캜 for 60 minutes. The peel strength (peel strength) of the plated conductor layer was measured for this circuit board.

<Measurement of Peel Strength (Peel Strength) of Plated Conductor Layer>

A partial notch having a width of 10 mm and a length of 100 mm was put in the conductor layer of the circuit board and the one end was peeled off and held with a tweezer (ACS-50C-SL, auto-comb type tester) And the load (kgf / cm) when 35 mm was peeled in the vertical direction at a rate of 50 mm / minute was measured.

&Lt; Measurement of arithmetic mean roughness (Ra value) and root mean square root roughness (Rq value) after harmonization >

Using a non-contact surface roughing machine (WYKO NT3300, manufactured by Vico Instruments), the Ra value and the Rq value were obtained from the values obtained by setting the measurement range to 121 mu m x 92 mu m by the VSI contact mode and the 50x magnification lens. Then, each of them was measured by randomly obtaining an average value of 10 points.

&Lt; Evaluation of PCT resistance &

The adhesive films produced in Examples and Comparative Examples were laminated on both surfaces of an inner layer circuit board using a batch type vacuum laminator MVLP-500 (trade name, manufactured by Meikisha Chemical Co., Ltd.). The laminate was subjected to pressure reduction for 30 seconds to set the air pressure to 13 hPa or less, and then press for 30 seconds at 100 占 폚 under a pressure of 0.74 MPa. After the PET film was peeled from the laminated adhesive film, the resin composition was cured at 190 DEG C for 1 hour to form an insulating layer. In addition, a PCT test (Pressure Cooker Test) was performed in which the sample was allowed to stand at 121.5 ° C and 100% RH for 100 hours using an advanced accelerated life testing apparatus (PM422 manufactured by ETAC). Thereafter, the temperature was returned to room temperature, and it was confirmed whether swelling occurred at the interface between the insulating layer and the underlying copper. Further, a cross cut (a lattice-shaped notch with a width of 1 mm) was put on the surface of the insulating layer to check whether the insulating layer was missing. The case where there was no swelling on the insulating layer and the copper-copper interface, and the case where the plugging did not occur after the crosscut was evaluated as &quot;&quot;, and the case where no swelling occurred on the insulating layer and the copper- Quot; DELTA &quot;, and the case where the insulating layer and the copper-based copper interface were swollen and the plugging occurred after the crosscut was evaluated as &quot; x &quot;.

&Lt; Measurement of carbon amount per unit area >

3 g of the surface-treated inorganic filler was used as a sample. The sample and 30 g of MEK (methyl ethyl ketone) were put in a centrifuge tube of a centrifugal separator, and the solid content was suspended by stirring to irradiate ultrasonic waves of 500 W for 5 minutes. Thereafter, solid-liquid separation (solid-liquid separation) was performed by centrifugation, and the supernatant was removed. Further, 30 g of MEK was added, and the mixture was stirred to suspend the solid content, and the mixture was irradiated with 500 W of ultrasonic waves for 5 minutes. Thereafter, solid-liquid separation was carried out by centrifugation, and the supernatant was removed. The solids were dried at 150 占 폚 for 30 minutes. 0.3 g of the dried sample was precisely weighed and placed in the crucible for measurement, and a combustion aid (3.0 g of tungsten, 0.3 g of tin) was further added to the crucible for measurement. The crucible for measurement was set in a carbon analyzer and the amount of carbon was measured. As the carbon analyzer, EMIA-320V manufactured by Horiba Seisakusho Co., Ltd. was used. The value obtained by dividing the measured carbon amount by the specific surface area of the inorganic filler was defined as the carbon amount per unit area.

&Lt; Preparation Example 1 &

100 parts by mass of spherical silica ("SOC2" manufactured by Adomex Co., Ltd., average particle diameter 0.5 μm) was added to a Henschel type honeycomb type mixer and mixed with N-benzylaminoethanol (manufactured by Tokyo Kasei Kogyo K.K. , Boiling point: 280 ° C), while stirring the spherical silica for 10 minutes to prepare a product 1 (amount of carbon per unit area of 0.13 mg / m 2).

&Lt; Preparation Example 2 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 μm) was added to the Henschel type honeycomb, and N-anilinoethanol (manufactured by Tokyo Kasei Kogyo K.K., boiling point 268 , 0.3 part by mass of methyl / phenyl group-containing alkoxy oligomer (&quot; X-40-9227 &quot; manufactured by Shin-Etsu Chemical Co., Ltd.) was stirred for 10 minutes while spraying, 2 (carbon amount per unit area: 0.25 mg / m 2).

&Lt; Preparation Example 3 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 탆) was added to the Henschel type honeycomb, and glycidol ("Epiol OH", manufactured by Nippon Oil Co., 167 占 폚), 0.3 part by mass of phenyltrimethoxysilane ("KBM-103" manufactured by Shin-Etsu Chemical Co., Ltd.) was stirred for 10 minutes while spraying, to obtain a product 3 And a carbon amount per unit area of 0.18 mg / m 2).

&Lt; Preparation Example 4 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 탆) was added to the Henschel type honeycomb, and N-benzylaminoethanol (manufactured by Tokyo Kasei Kogyo K.K., boiling point 280 , And 0.3 part by mass of phenyltrimethoxysilane ("KBM-103" manufactured by Shin-Etsu Chemical Co., Ltd.) was stirred for 10 minutes while spraying, to obtain a product 4 And a carbon amount per area of 0.27 mg / m 2).

&Lt; Production Example 5 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 탆) was added to the Henschel type honeycomb, and N-benzylaminoethanol (manufactured by Tokyo Kasei Kogyo K.K., boiling point 280 ) Was stirred for 10 minutes while 0.3 part by mass of a methyl group-containing alkoxy oligomer ("MTMS-A" manufactured by Tama Chemical Co., Ltd.) was sprayed for 5 minutes while spraying, to obtain a product 5 0.18 mg / m &lt; 2 &gt;).

&Lt; Production Example 6 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 탆) was placed in a Henschel-type honeycomb filter and immersed in an imidazole-epoxy duct ("P200" manufactured by Mitsubishi Kagaku Kogyo K.K.) , 0.9 part by mass of a nonvolatile component 30% cyclohexane solution) was sprayed on the spherical silica for 10 minutes while spraying, 0.3 parts by mass of a methyl group-containing alkoxy oligomer ("MTMS-A" manufactured by Tama Gaku Kagaku Co., Ltd.) And the mixture was stirred to produce Preparation 6 (carbon content per unit area of 0.29 mg / m 2).

&Lt; Production Example 7 >

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 μm) was added to the Henschel type honeycomb, and 2,2 - [{(methyl-1H-benzotriazole- , 0.5 part by mass of methyl ethyl ketone (TT-LYK manufactured by JOHOKU KAGAKU KOGYO CO., LTD., MEK solution of non-volatile component 60%) was sprayed on the spherical silica for 10 minutes, , And 0.3 part by mass of an oligomer ("MTMS-A" manufactured by Tama Gaku Kagaku Co., Ltd.) were stirred for 5 minutes while spraying to prepare a product 7 (amount of carbon per unit area: 0.16 mg / m 2).

&Lt; Production Example 8 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 μm) was added to the Henschel type honeycomb, and 2,2 - [{(methyl-1H-benzotriazole- (TT-LYK manufactured by JOHOKU KAGAKU KOGYO CO., LTD., MEK solution of 60% non-volatile component) 0.5 part by mass was sprayed on the spherical silica for 10 minutes, And 0.3 part by mass of a coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) were stirred for 5 minutes while spraying, to prepare a product 8 (carbon content per unit area of 0.32 mg / m 2).

&Lt; Production Example 9 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 μm) was added to the Henschel type honeycomb, and 1- (2-hydroxyethyl) imidazole (Manufactured by Shin-Etsu Chemical Co., Ltd., product of Shin-Etsu Chemical Co., Ltd., manufactured by Shinetsu Kagaku Kogyo K.K.), 0.5 part by mass of a nonvolatile component (60% KBE-22 &quot;) were stirred for 10 minutes while spraying, to prepare a product 9 (amount of carbon per unit area: 0.12 g / m 2).

&Lt; Production Example 10 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 μm) was added to the Henschel type hornblend, and phenyltrimethoxysilane ("KBM- 103 &quot;, boiling point: 218 占 폚) were stirred for 10 minutes while spraying, to prepare a product 10 (carbon content per unit area: 0.09 mg / m 2).

&Lt; Production Example 11 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 탆) was added to the Henschel type honeycomb, and an epoxy group-containing silane coupling agent (KBM403, manufactured by Shinetsu Kagaku Kogyo K.K.) , Boiling point: 290 占 폚) were stirred for 5 minutes while spraying, to thereby prepare Production 11 (carbon content per unit area of 0.24 mg / m 2).

&Lt; Production Example 12 &

100 parts by mass of spherical silica ("SC2050-SQ" manufactured by Adomex Co., Ltd., average particle diameter 0.5 탆) was charged in a Henschel-type mixed sieve and an amino group-containing silane coupling agent (KBM903, manufactured by Shinetsu Kagaku Kogyo K.K.) , Boiling point 215 占 폚) (0.6 parts by mass) was stirred for 5 minutes while spraying to prepare a product 12 (amount of carbon per unit area of 0.14 mg / m 2).

&Lt; Example 1 >

14 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, 5 parts by mass of "HP4700" manufactured by DIC Corporation), liquid bisphenol A type epoxy resin (epoxy equivalent 180, "jER828EL" manufactured by Mitsubishi Chemical Corporation) And 14 parts by mass of an epoxy resin (epoxy equivalent 269, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.) were dissolved by heating in 30 parts by mass of solvent naphtha with stirring and then cooled to room temperature to prepare a mixture 1. Then, And 1.5 parts by mass of particles (STABILLOID AC3816N, manufactured by Ganz Chemical Co., Ltd.) were swollen at 6 DEG C for 12 hours at 20 DEG C to prepare Mixture 2. To Mixture 1, Mixture 2 and Product 1 were added (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, manufactured by Sankyo Kagaku Co., Average particle size 1 占 퐉), and the resulting mixture was kneaded in three rolls to be uniformly dispersed. A phenol novolac type curing agent ("LA-7054" manufactured by DIC Corporation) 10 parts by mass of a norbornene-based phenolic resin (phenolic hydroxyl group equivalent 215, "SN485" manufactured by Shin-Etsu Chemical Co., Ltd., MEK solution of 60% by mass of a nonvolatile component) 10 parts by mass , 7 parts by mass of a phenoxy resin (weight average molecular weight 35000, "YL7553" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone in a nonvolatile component 30% by mass), 4-dimethylamino 2 parts by mass of a 5% by mass MEK solution of pyridine and 4 parts by mass of MEK were mixed and uniformly dispersed by a rotary mixer to prepare a resin varnish. Next, this resin varnish was applied to a polyethylene terephthalate film 38 [micro] m) The coated layer was uniformly coated with a die coater so that the thickness of the resin composition layer after drying was 40 占 퐉 and dried at 80 to 110 占 폚 (average 95 占 폚) for 5 minutes (amount of residual solvent in the resin composition layer: about 2 mass %). Next, a polypropylene film having a thickness of 15 mu m was adhered to the surface of the resin composition layer, and the film was wound in a rolled form. The rolled adhesive film was slit at a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 x 336 mm.

&Lt; Example 2 >

A resin varnish was produced in the same manner as in Example 1, except that the product 1 was changed to the product 2. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Example 3 >

A resin varnish was produced in the same manner as in Example 1, except that the preparation 1 was changed to the preparation 3. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

<Example 4>

A resin varnish was produced in exactly the same manner as in Example 1 except that the preparation 1 was changed to the preparation 4. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Example 5 >

A resin varnish was produced in the same manner as in Example 1 except that the preparation 1 was changed to the preparation 5. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Example 6 >

A resin varnish was produced in the same manner as in Example 1 except that the preparation 1 was changed to the preparation 6. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Example 7 >

A resin varnish was produced in the same manner as in Example 1 except that the preparation 1 was changed to the preparation 7. [ Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Example 8 >

A resin varnish was prepared in exactly the same manner as in Example 1 except that the preparation 1 was changed to the preparation 8. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Example 9 >

A resin varnish was produced in the same manner as in Example 1 except that the preparation 1 was changed to the preparation 9. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Example 10 >

, 10 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, "EXA4032SS" manufactured by DIC Corporation), 1 part by mass of a beacilene type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 12 parts by mass of epoxy-type epoxy resin (epoxy equivalent of about 330, "ESN475V" manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved by heating in 20 parts by mass of solvent naphtha with stirring and then cooled to room temperature to prepare Mixture 3. Subsequently, 1.5 parts by mass of rubber particles (STABILLOID AC3816N manufactured by KANSEI CHEMICAL CO., LTD.) Were allowed to undergo constant swelling in 6 parts by mass of solvent naphtha at 20 占 폚 for 12 hours to prepare Mixture 4. To the mixture 3, the mixture 4 and the product 4 were added, and a flame retardant ("HCA-HQ", 10- (2,5-dihydroxyphenyl) -10-hydro-9- -Phosphophenanthrene-10-oxide, average particle diameter 1 占 퐉) were added, and the mixture was kneaded with three rolls and dispersed uniformly. 10 parts by mass of an active ester type curing agent (active equivalent weight: about 223, "HPC-8000-65T" manufactured by DIC Corporation), 10 parts by mass of a toluene solution of a nonvolatile component of 65% by mass, , 10 parts by mass of a non-volatile component (a 1: 1 solution of MEK and cyclohexanone in a volume ratio of 30% by mass), 11 parts by mass of bisphenol A dicyanate (Primaset BADCy manufactured by Lonza Japan K.K.) And 0.6 mass parts of a 5 mass% MEK solution of 4-dimethylaminopyridine as a curing accelerator and 1 mass of cobalt (III) acetylacetonate (Co (III) AcAc, manufactured by Tokyo Chemical Industry Co., Ltd.) % Of MEK solution were mixed and uniformly dispersed with a rotary mixer to prepare a resin varnish. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Comparative Example 1 &

Except that the product 1 of Example 1 was changed to 100 parts by mass of spherical silica (&quot; SOC2 &quot; manufactured by Adomex Co., Ltd., average particle diameter 0.5 占 퐉) to prepare a resin varnish. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Comparative Example 2 &

Preparation 1 of Example 1 was changed to 100 parts by mass of spherical silica (&quot; SOC2 &quot; manufactured by Adomex Corp., average particle diameter 0.5 占 퐉), and N-benzylaminoethanol (manufactured by Tokyo Kasei Kogyo K.K.) Was added in an amount of 0.3 part by mass to prepare a resin varnish. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Comparative Example 3 &

A resin varnish was prepared in exactly the same manner as in Example 1, except that the preparation 1 was changed to the preparation 10. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Comparative Example 4 &

A resin varnish was prepared in exactly the same manner as in Example 1 except that the preparation 1 was changed to the preparation 11. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

&Lt; Comparative Example 5 &

A resin varnish was produced in the same manner as in Example 1, except that the preparation 1 was changed to the preparation 12. Next, the resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.

The results are shown in Table 1.

From the results shown in Table 1, it can be seen that the resin compositions of Examples 1 to 10 have PCT resistance, a low arithmetic mean roughness, and a low root mean square root roughness, and a sufficient value of the fill strength is obtained. On the other hand, in Comparative Examples 1 to 5, the PCT resistance was lowered, the arithmetic mean roughness and the root mean square roughness became larger, and the plating became swollen to a remarkably small value.

It is possible to form a plated conductor layer having a small arithmetic mean roughness and a root mean square roughness of the surface of the insulating layer and a sufficient fill strength in the wet roughening step and to provide a resin composition having PCT resistance. It is also possible to provide an adhesive film, a prepreg, a multilayer printed wiring board and a semiconductor device using the same. In addition, it is possible to provide vehicles such as computers, mobile phones, digital cameras, televisions and the like equipped with these, motorcycles, cars, tanks, ships, and aircraft.

Claims (10)

A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the inorganic filler is surface-treated with an organic compound having a hydroxyl group and a reactive group and a boiling point of 100 ° C or higher, Wherein the reactive group of the compound is at least one member selected from the group consisting of an amino group and an epoxy group. The organic electroluminescent device according to claim 1, wherein the organic compound is at least one compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), an imidazole compound and an imidazole- .
Formula 1

(2)

(3)

In the above Chemical Formulas 1 to 3,
R1 and R2 each independently represent a phenyl group, a benzyl group, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R3 is an alkylene group having 1 to 5 carbon atoms or a phenylene group,
R4 is an alkylene group or a phenylene group having 1 to 5 carbon atoms,
R5 is an organic group having a hydroxy group,
R6 is a hydrogen atom, a methyl group, a carboxyl group or a phenyl group. The resin composition according to claim 1, wherein the organic compound (C) is 0.05 to 2% by mass when the inorganic filler is 100% by mass. The method according to claim 1, wherein after the inorganic filler (C) is surface-treated with the organic compound, a group consisting of a silane coupling agent, an alkoxysilane, an alkoxy oligomer, an aluminum based coupling agent, a titanium based coupling agent and a zirconium based coupling agent And the surface of the resin composition is at least one selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol. The resin composition according to claim 1, wherein the amount of carbon bonded to the surface of the inorganic filler (C) is 0.05 to 1.00 mg / m 2 per unit area. The method for manufacturing a semiconductor device according to claim 1, wherein the resin composition is cured to form an insulating layer, the surface of the insulating layer is roughened, and the conductor layer and the insulating layer obtained by plating have a fill strength of 0.4 kgf / cm to 1.5 kgf / Cm, an insulating layer is formed by curing the resin composition, an arithmetic mean roughness after roughening the surface of the insulating layer is 10 nm to 300 nm, a root mean square roughness of the root mean square is 10 nm to 480 nm, (Successively soaking) the surface of the insulating layer in a swelling liquid at 50 to 80 캜 for 5 to 20 minutes, an oxidizing agent at 60 to 80 캜 for 10 to 30 minutes and a neutralizing liquid at 30 to 50 캜 for 3 to 10 minutes, Wherein the resin composition is a resin composition. A sheet-stacked material characterized by containing the resin composition according to any one of claims 1 to 6. A multilayer printed wiring board in which an insulating layer is formed by a cured product of the resin composition according to any one of claims 1 to 6. A semiconductor device characterized by using the multilayered printed circuit board according to claim 8. delete