TWI629306B - Resin composition - Google Patents

Abstract

An object of the present invention is to provide a resin composition which is a hardened product having a high peeling strength despite being low in linear thermal expansion coefficient and low roughness, and can constitute a sheet-like laminated material having excellent lamination properties.

This solution is a resin composition containing (A) an epoxy resin, (B) a hardener, and (C) a filler having an average linear thermal expansion coefficient of 300 ppb / ° C from 30 ° C to 150 ° C.

Description

Resin composition

The present invention relates to a resin composition.

Multilayer printed circuit boards are widely used in various electronic machines. Electronic parts. As a manufacturing technology of a multilayer printed wiring board, a manufacturing method of an inner layer circuit substrate provided with a circuit conductor by a method of stacking an insulating layer and a conductor layer alternately is known.

The manufacturing method by the stacking method is generally carried out in the following order. First, a resin composition layer is provided on the inner circuit board, and the resin composition layer is hardened to form an insulating layer. Next, the surface of the insulating layer is swollen with a swelling liquid, and then roughened with an oxidizing agent to form minute irregularities on the surface of the insulating layer. Thereafter, a conductive layer having a specific wiring pattern is formed on the surface of the insulating layer according to a known method such as a semi-additive method.

In recent years, when manufacturing a multilayer printed circuit board, in order to prevent interlayer peeling or wiring breakage due to the difference in thermal expansion between the insulating layer and the conductor layer, the interlayer insulating material has been required to have a low linear thermal expansion rate. The resin composition is filled with a high filler to reduce the linear thermal expansion coefficient (for example, Patent Document 1 and Patent Document 2).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-38821

[Patent Document 2] Japanese Patent Laid-Open No. 2006-4854

The present inventors have studied conventional fillers and found that as the filling amount increases, there is a problem that melt viscosity or surface roughness tends to increase, and formation of fine wiring becomes difficult.

An object of the present invention is to provide a resin composition which is a hardened product having a high peeling strength despite being low in linear thermal expansion coefficient and low roughness, and can constitute a sheet-like laminated material having excellent lamination properties.

The present inventors have repeatedly studied in view of the above-mentioned problems, and found that the average linear thermal expansion coefficient from 30 ° C to 150 ° C can be 300 ppb / by using (A) epoxy resin, (B) hardener, and (C). A resin composition of a filler at a temperature lower than ℃ solves the above problems, and finally completes the present invention.

That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) a hardener, and (C) an average linear thermal expansion coefficient from 30 ° C to 150 ° C Fillers below 300ppb / ℃.

[2] The resin composition according to [1], wherein when the non-volatile content in the resin composition is 100% by volume, 5 to 80% by volume (C) is included between 30 ° C and 150 ° C. Filler with an average linear thermal expansion coefficient of 300 ppb / ° C or less.

[3] The resin composition according to [1] or [2], wherein (C) the average particle diameter of the filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C of 300 ppb / ° C or less is 0.01 to 10 μm .

[4] The resin composition according to any one of [1] to [3], in which the specific gravity of the filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C of 300 ppb / ° C is 1 to 7g / cm ³ .

[5] The resin composition according to any one of [1] to [4], wherein (C) the filler having an average linear thermal expansion coefficient from 30 ° C to 150 ° C of 300 ppb / ° C or less is a spherical inorganic filler Or broken inorganic filler.

[6] The resin composition according to any one of [1] to [5], wherein (C) the filler having an average linear thermal expansion coefficient from 30 ° C to 150 ° C of 300 ppb / ° C or less is selected from glass fillers And one or more of the zirconium phosphate-based fillers.

[7] The resin composition according to any one of [1] to [6], wherein (C) the filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C of 300 ppb / ° C or lower is a doped titanium type Glass filler.

[8] The resin composition according to any one of [1] to [7], wherein (B) the hardener is selected from an active ester hardener, a cyanate ester hardener, a phenol hardener, and naphthalene One or more of phenolic hardeners.

[9] The resin composition according to any one of [1] to [8], wherein (A) The epoxy resin is a bisphenol A epoxy resin, a biphenylaralkyl epoxy resin, a naphthol epoxy resin, a naphthalene epoxy resin, a naphthalene ether epoxy resin, or two or more of these The mixture, (B) a hardener-based active ester-based hardener, and (C) a filler having an average linear thermal expansion coefficient from 30 ° C to 150 ° C of 300 ppb / ° C or lower are doped titanium-type glass fillers.

[10] The resin composition according to any one of [1] to [9], wherein the average linear thermal expansion coefficient of the hardened material of the resin composition from 25 ° C to 150 ° C is 20 ppm or less, and Ra of the surface of the hardened object after the roughening treatment is 400 nm or less, and a hardened object of the resin composition is formed. On the surface of the hardened object after the roughening treatment of the hardened object, a conductor layer is formed by plating. The plating peel strength of the object surface and the conductor layer is 0.4 kgf / cm or more.

[11] The resin composition according to any one of [1] to [10], which is used for an insulating layer of a multilayer printed circuit board.

[12] An adhesive film comprising the resin composition according to any one of [1] to [11].

[13] The adhesive film according to [12], wherein the melt viscosity of the resin composition layer of the adhesive film at 100 ° C. is 35,000 poise or less.

[14] A cured product, which is a resin composition according to any one of [1] to [11].

[15] The cured product according to [14], wherein the average linear thermal expansion coefficient from 25 ° C to 150 ° C is 20 ppm or less.

[16] The hardened product according to [14] or [15], wherein Ra of the surface of the hardened product after the roughening treatment is 400 nm or less.

[17] The hardened material according to any one of [14] to [16], wherein when the surface of the hardened material after the roughening treatment of the hardened material is formed by plating, the surface of the hardened material and the conductive layer The plating peeling strength is 0.4 kgf / cm or more.

[18] A multilayer printed circuit board having a hardened body as described in any one of [14] to [17].

[19] A semiconductor device using the multilayer printed circuit board according to [18].

[20] A resin composition for an insulating layer of a multilayer printed circuit board, which comprises (A) an epoxy resin, (B) a hardener, and (C) an average linear thermal expansion coefficient from 30 ° C to 150 ° C The resin composition for an insulating layer of a multilayer printed wiring board having a filler of 300 ppb / ° C or less is characterized in that the (A) epoxy resin is a bisphenol A type epoxy resin, a biphenylaralkyl type epoxy resin, Naphthol-type epoxy resin, naphthalene-type epoxy resin, naphthyl ether-type epoxy resin, or a mixture of two or more thereof, the (B) hardener is an active ester-based hardener, and the (C) is from 30 ° C. The filler with an average linear thermal expansion coefficient of 300 ppb / ° C to 150 ° C is a doped titanium-type glass filler. The average linear thermal expansion coefficient of the hardened body of the resin composition from 25 ° C to 150 ° C is 20 ppm or less. The resin Ra of the surface of the hardened material of the composition after the roughening treatment is 400 nm or less, and A hardened body of the resin composition is formed, and a conductor layer is formed by plating on a surface of the hardened body after the roughening treatment of the hardened body, and the peeling strength of the hardened body surface and the conductive layer is 0.4 kgf / cm or more.

According to the present invention, it is possible to provide a resin composition which is a hardened product having a high peeling strength and has a low linear thermal expansion coefficient and a low roughness, and can constitute a sheet-like laminated material having excellent lamination properties.

The resin composition of the present invention is a filler containing (A) an epoxy resin, (B) a hardener, and (C) an average linear thermal expansion coefficient of 300 ppb / ° C from 30 ° C to 150 ° C.

<(A) epoxy resin>

Examples of the "epoxy resin" used in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentadiene. Ethylene type epoxy resin, ginseng phenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthalene 4-functional Epoxy resin, naphthol epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, Biphenyl epoxy resin, biphenylaralkyl epoxy resin, linear aliphatic epoxy resin, butadiene structure Epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiral epoxy resins, cyclohexanedimethanol epoxy resins, naphthalene ether epoxy resins and trimethylol ring Oxygen resin and so on. Among them, bisphenol A type epoxy resin, biphenylaralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalene ether type epoxy resin, and two or more of these are preferred. mixture. The epoxy resin may be used singly or in combination of two or more kinds.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is 100% by mass, the epoxy resin having two or more epoxy groups in one molecule is preferably at least 50% by mass or more.

In addition, it is preferable to include an epoxy resin in a liquid state at a temperature of 20 ° C (hereinafter referred to as a "liquid epoxy resin") and an epoxy resin in a solid shape at a temperature of 20 ° C (hereinafter referred to as a "solid shaped ring" Oxygen resin "). As the epoxy resin, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin in combination. The breaking strength of the insulating layer formed by curing the resin composition is also increased.

The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolac epoxy resin, or a naphthalene epoxy resin, and more preferably a bisphenol A epoxy resin. Resin, bisphenol F-type epoxy resin, or naphthalene-type epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "EXA4032SS", "HP4032SS" (naphthalene-type epoxy resin), and "jER828EL" manufactured by Mitsubishi Chemical Corporation. "(Bisphenol A type epoxy resin)," jER807 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac Lacquer-type epoxy resin), "ZX1059" (mixed product of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., etc. As the liquid epoxy resin, "HP4032SS" (naphthalene type epoxy resin) and "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) are particularly preferable. Liquid epoxy resin can be used alone or in combination of two or more

As the solid epoxy resin, a 4-functional naphthalene epoxy resin, a cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, a ginseng phenol epoxy resin, a naphthol novolac epoxy resin, Biphenyl type epoxy resin or naphthyl ether type epoxy resin, more preferably 4-functional naphthalene type epoxy resin, biphenyl type epoxy resin, or naphthyl ether type epoxy resin, and even more preferably biphenyl type epoxy resin Resin. Specific examples of the solid epoxy resin include "HP-4700", "HP-4710" (4-functional naphthalene-type epoxy resin), and "N-690" (cresol novolac type) made by DIC. Epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200", "HP7200H", "HP7200K-65I" (dicyclopentadiene epoxy resin), "EXA7311" , "EXA7311-G3", "EXA7311-G4", "HP6000" (naphthalene ether type epoxy resin), "EPPN-502H" (ginseng phenol epoxy resin) made by Nippon Kayaku Co., Ltd., and "NC7000L" ( Naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol novolac resin) made by Nippon Steel Chemical Co., Ltd. Type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H" made by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bimethicone) (Phenolic epoxy resin) Wait. In particular, `` YX4000HK '' (bixylenol-type epoxy resin), `` NC3000L '' (biphenyl-type epoxy resin), and `` HP7200H '' (dicyclopentyl) manufactured by DIC (stock) Ethylene type epoxy resin) is preferred. The solid epoxy resin may be used singly or in combination of two or more kinds.

When the liquid epoxy resin and the solid epoxy resin are used together as an epoxy resin, the quantity ratio (liquid epoxy resin: solid epoxy resin) with a better quality is 1: 0.1 to 1: 4. range. By setting the ratio of the amount of the liquid epoxy resin to the solid epoxy resin within this range, it is obtained that: i) when the film is used in the form of an adhesive film, it imparts moderate adhesiveness, and ii) when it is used in the form of a film. To obtain sufficient flexibility and improve operability, and iii) to obtain the effect of an insulating layer and the like having sufficient breaking strength. From the viewpoint of the effects of i) to iii) described above, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1: The range is from 0.3 to 1: 3.5, more preferably from 1: 0.6 to 1: 3, and particularly preferably from 1: 0.8 to 1: 2.5.

The content of the epoxy resin in the resin composition is preferably 20% to 50% by mass, and more preferably 25% to 45% by mass when the non-volatile content in the resin composition is set to 100% by mass. More preferably, it is 30% to 40% by mass.

The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, and even more preferably 110 to 1,000. By setting it as this range, the insulating layer which has sufficient crosslinking density of hardened | cured material and low surface roughness will be brought. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of a resin containing 1 equivalent of epoxy groups.

<(B) Hardener>

The hardening agent is not particularly limited as long as it has a function of hardening the epoxy resin, but examples thereof include an active ester hardener, a cyanate ester hardener, a phenol hardener, a naphthol hardener, and benzoxamine. Azine-based hardeners and the like. Among them, it is preferred to use one or more selected from the group consisting of an active ester-based hardener, a cyanate-ester-based hardener, a phenol-based hardener, and a naphthol-based hardener, and more preferably an active ester-based hardener. The hardener may be used alone or in combination of two or more.

Although it is not particularly limited as the active ester-based hardener, it is generally preferred to use a reaction having two or more phenol esters, thiophenol esters, N-hydroxylamine esters, and heterocyclic hydroxyl compounds in one molecule. Highly active ester-based compounds. The active ester-based hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. hardener. 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, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methylol Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-bis Hydroxynaphthalene, 2,6-dihydroxynaphthalene, di Hydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, Benzenetriol, dicyclopentadienyl diphenol, phenol novolac, and the like.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol condensation structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetic acid compound of phenol novolac, and a benzyl compound containing phenol novolac are preferred. The ammonium active ester compound is more preferably an active ester compound containing a dicyclopentadiene-type diphenol condensation structure.

As an active ester hardener containing a dicyclopentadiene-type diphenol condensation structure, the compound represented by following formula (1) is mentioned more specifically.

In the formula (1), two R's are each independently a phenyl group or a naphthyl group. k represents 0 or 1. The average of n in repeating units is 0.05 to 2.5.

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

As commercially available products of the active ester-based hardener, examples of the active ester compound containing a dicyclopentadiene-type diphenol condensation structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (DIC (Manufactured by the company), and examples of the active ester compound containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC) is an active ester compound containing an acetic acid compound of phenol novolac, and "DC808" (manufactured by Mitsubishi Chemical Corporation) is a benzamidine containing a novolac Examples of the active ester compound of the compound include "YLH1026" (manufactured by Mitsubishi Chemical Corporation) and the like.

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), and 4,4 '-Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2 -Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatebenzyl), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3 -Bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether Bifunctional cyanate resins, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, etc., and triazinated prepolymers which are part of these cyanate resins. Preferred specific examples of the cyanate ester-based hardener include "PT30" and "PT60" (both of which are phenol novolac-type polyfunctional cyanate resins) and "BA230" made by Lonza Japan. (Part or all of the bisphenol A dicyanate becomes a prepolymer of a triazinated terpolymer) and the like.

As the phenol-based hardener and naphthol-based hardener, from the viewpoint of heat resistance, a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure is preferred. From the standpoint of adhesion with the conductor layer (circuit wiring), a nitrogen-containing phenol-based hardener is preferred, and a triazine skeleton-containing phenol-based hardener is more preferred. Among these, from the standpoint of heat resistance and adhesion (peel strength) to the conductor layer, it is preferred to contain triazine bone Shelf phenol novolac resin is used as a hardener.

Specific examples of the phenol-based hardener and naphthol-based hardener include, for example, "MEH-7700", "MEH-7810", "MEH-7851", manufactured by Nippon Kasei Co., Ltd., and manufactured by Nippon Kayakusho Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" "," LA7052 "," LA7054 "," LA3018 ", etc. of the DIC system.

Specific examples of the benzoxazine-based hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

The amount of the hardener in the resin composition is not particularly limited as long as it can harden the epoxy resin, but when the nonvolatile content in the resin composition is 100% by mass, for example, 15 to 50% by mass, preferably 20 ~ 45 mass%, more preferably 25 to 40 mass%.

<(C) A filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C of 300 ppb / ° C or less>

As a method for measuring the average linear thermal expansion coefficient of the filler from 30 ° C to 150 ° C, for example, a thermal dilatometer that can detect the extension of the sample by a laser interferometer or a known method such as an X-ray diffraction method can be used for the measurement. .

As the "filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C or below 300 ppb / ° C", an inorganic filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C or below 300 ppb / ° C is more preferred, and more Good for Spherical inorganic fillers and crushed inorganic fillers having an average linear thermal expansion coefficient of 300 ppb / ° C or lower between 30 ° C and 150 ° C, and even more preferably an average linear thermal expansion coefficient of 300 ppb / ° C or lower from 30 ° C to 150 ° C Spherical inorganic filler. Specific examples include glass fillers, zirconium phosphate-based fillers, cordierite-based fillers, silicon oxide-based fillers, and zirconium tungstate-based fillers having an average linear thermal expansion coefficient of 300 ppb / ° C or lower from 30 ° C to 150 ° C. Fillers, and manganese nitride-based fillers. Among them, it is preferable to use at least one selected from the group consisting of glass fillers and zirconium phosphate-based fillers from the point that the cured product can have a low roughness or the melt viscosity of the adhesive film can be reduced. The glass filler is preferably a doped titanium type glass filler, and more preferably a doped titanium type glass filler.

Examples of the titanium-doped glass filler include, for example, TiCl ₄ and SiCl ₄ which are glass-forming raw materials of TiO ₂ -SiO ₂ glass, which are respectively gasified and mixed, and are heated and hydrolyzed by a hydrogen-oxygen flame (flame). Hydrolysis) of the obtained TiO ₂ -SiO ₂ glass fine particles. The doped titanium-type glass filler can be produced by the method described in International Publication No. 2010/134449. As an example of a commercially available product, "AZ filler" (linear thermal expansion coefficient ( 30-150 ° C average value): 0.2ppm / ° C doped titanium spherical glass filler). Examples of the commercially available products of the zirconium phosphate-based filler include "ZWP" (linear thermal expansion coefficient (average value of 30-150 ° C): -0.3 ppm / ° C) made by KCM (stock). As an example of the commercial product of the said broken glass filler, the "DL7400" (linear thermal expansion coefficient (average value of 30-150 degreeC): -1.1 ppm / degreeC) by the Japan Electric Glass Co., Ltd. is mentioned.

(C) The average linear thermal expansion rate from 30 ° C to 150 ° C The average particle diameter of the filler below 300 ppb / ° C is from the viewpoint of making the cured product low in roughness and making fine wiring possible, or improving the fluidity of the resin composition to improve lamination, A range of 0.01 μm to 10 μm is preferred, a range of 0.05 μm to 8 μm is more preferred, a range of 0.1 μm to 5 μm is even more preferred, and a range of 0.2 μm to 3 μm is even more preferred. The average particle diameter of the filler can be diffracted by laser according to Mie scattering theory. Scattering method. Specifically, the particle size distribution of the filler is prepared on a volume basis by a laser diffraction scattering particle size distribution measurement device, and the median diameter can be measured as the average particle diameter. As the measurement sample, it is preferable to use a material in which the filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring device, LA-500 manufactured by Horiba, etc. can be used.

(C) from an average linear thermal expansion coefficient between 30 deg.] C to 150 deg.] C to a specific gravity 300ppb / ℃ or less of the filler, the separation preventing varnish, the film uniformity of the composition in view, preferably 1g / cm ³ ~ The range of 7 g / cm ³ is more preferably a range of 1 g / cm ³ to 5 g / cm ³ , and still more preferably a range of 1.5 g / cm ³ to 3 g / cm ³ .

(C) The content of the filler having an average linear thermal expansion coefficient from 30 ° C to 150 ° C of 300 ppb / ° C or lower, from the viewpoint of low thermal expansion of the hardened material when the nonvolatile content in the resin composition is set to 100% by volume From the viewpoint, it is preferably 5 vol% or more, more preferably 10 vol% or more, and even more preferably 15 vol% or more. From the viewpoint of fluidity of the resin composition, it is preferably 80% by volume or less, more preferably 70% by volume or less, and even more preferably 65% by volume or less.

The resin composition of the present invention may contain, as necessary, a filler having an average linear thermal expansion coefficient of 300 ppb / ° C or less from (C) from 30 ° C to 150 ° C, and other fillers, if necessary. .

Examples of fillers other than those having an average linear thermal expansion coefficient of 300 ppb / ° C from 30 ° C to 150 ° C include silicon dioxide having an average linear thermal expansion coefficient of 300 ppb / ° C from 30 ° C to 150 ° C. , Alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate , Magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, particularly suitable are silicon dioxide such as amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, and the like. As the silicon dioxide, spherical silicon dioxide is preferable. The filler may be used singly or in combination of two or more kinds. Examples of commercially available spherical fused silica include "SOC2" (average linear thermal expansion coefficient from 30 ° C to 150 ° C: 0.5ppm / ° C) manufactured by Admatechs, and "SOC1" (from 30 ° C to Average linear thermal expansion rate between 150 ° C: 0.5 ppm / ° C).

(C) The volume ratio of a filler having an average linear thermal expansion coefficient from 30 ° C to 150 ° C of 300 ppb / ° C or less and a filler other than the filler is, for example, 100: 0 to 10:90, preferably 100: 0 ~ 20: 80, more preferably 100: 0 ~ 30: 70.

In the resin composition of the present invention, the content of the total filler (the average linear thermal expansion coefficient from 30 ° C to 150 ° C is 300 ppb / ° C or less The total content of the filler and other fillers) is 100% by volume of the nonvolatile component in the resin composition. From the viewpoint of low thermal expansion of the cured product, it is preferably 40% by volume or more, and more preferably 50% by volume. the above. From the viewpoint of fluidity at the time of lamination of the resin composition, it is preferably 80% by volume or less, more preferably 70% by volume or less, and even more preferably 65% by volume or less.

In order to improve the moisture resistance and dispersibility of the filler, a silane coupling agent (epoxy silane coupling agent, amine silane coupling agent, mercapto silane coupling agent, etc.), titanate coupling agent, and silicon nitrogen are preferably used. Surface treatment agents such as alkane compounds are surface-treated. These can be used singly or in combination of two or more kinds.

Examples of the epoxy silane-based coupling agent include glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, glycidyloxypropylmethyldiethoxysilane, and glycidyl Examples of the aminosilane-based coupling agent include butyltrimethoxysilane and (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and examples thereof include aminopropylmethoxysilane and aminopropyltrisilane. Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, etc., as the mercaptosilane coupling agent, for example, may be Examples include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, and the like. These can be used singly or in combination of two or more kinds. Examples of commercially available coupling agents include "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM803" (3-mercaptopropane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Alkane), "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and the like.

The resin composition of the present invention further contains the following other components, and may include additives such as a thermoplastic resin, a hardening accelerator, and a flame retardant, for example.

-Thermoplastic resin-

Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyimide resin, a polyetherimide resin, and a polyimide resin. The thermoplastic resin may be used singly or in combination of two or more kinds.

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

Examples of the phenoxy resin include a resin selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, and a dicyclopentadiene skeleton. One or more types of phenoxy resins in a group consisting of a frame, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be a functional group such as a phenolic hydroxyl group or an epoxy group. One type of phenoxy resin may be used alone, or two or more types may be used in combination. Specific examples of the phenoxy resin include "1256" and "4250" (both of which are phenoxy resins containing a bisphenol A skeleton) and "YX8100" (containing bisphenol S) manufactured by Mitsubishi Chemical Corporation. Phenoxy resin with skeleton) and "YX6954" (phenoxy resin with bisphenol acetophenone skeleton), others can also include "FX280" and "FX293" made by Toto Kasei Co., Ltd., and Mitsubishi Chemical (stock ) "YL7553", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

Specific examples of the polyvinyl acetal resin include electrochemical butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Sekisui Chemical Industry Co., Ltd., and EslecBH series manufactured by Sekisui Chemical Industry Co., Ltd. , BX series, KS series, BL series, BM series, etc.

Specific examples of the polyimide resin include "RIKACOATSN20" and "RIKACOATPN20" manufactured by Nippon Rika Co., Ltd. Specific examples of the polyfluorene imide resin include a linear polyfluorene imide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic anhydride (Japanese Patent Laid-Open No. 2006-37083 Those described), modified polyimide containing a polysiloxane skeleton (described in Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386), and the like.

Specific examples of the polyamidamine / imide resin include Toyo "VylomaxHR11NN" and "VylomaxHR16NN" based on the textile industry. As specific examples of the polyamidoamine imine resin, modified polyamidoamines such as the polyamidoamine imide “KS9100” and “KS9300” containing a polysiloxane skeleton manufactured by Hitachi Chemical Industries, Ltd. can also be cited.醯 imine.

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

Specific examples of the polyfluorene resin include polyfluoride "P1700" and "P3500" made by Solvay Advanced Polymers.

When the content of the thermoplastic resin in the resin composition is set to 100% by mass of the nonvolatile component in the resin composition, it is preferably 0.1% to 20% by mass, and more preferably 0.5% to 10% by mass. By setting the content of the thermoplastic resin to this range, a resin composition having a moderate viscosity and a uniform thickness or bulk properties can be formed.

-Hardening accelerator-

Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Preferred are amine-based hardening accelerators and imidazole-based hardening accelerators. Hardening accelerator, metal-based hardening accelerator.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, osmium borate compounds, tetraphenyl osmium tetraphenyl borates, n-butyl osmium tetraphenyl borates, and tetrabutyl osmium decane. Acid salt, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate And the like, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-ginseng (dimethyl Aminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4. 0] -undecene.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4- Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitic acid, 1-cyanoethyl-2-phenylimidazolium trimellitide Acid, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-deca Monoalkylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] -Ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2 -Phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro- 1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2- 3-benzyl imidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the like, and an adduct of an imidazole compound and an epoxy resin, preferably 2-ethyl-4- Methylimidazole, 1-benzyl-2-phenylimidazole.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramine Methylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-bis Ethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide, etc., preferably dicyandiamide, 1,5,7-triazine Bicyclo [4.4.0] dec-5-ene.

The metal-based hardening accelerator is not particularly limited, but examples thereof include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetopyruvate, cobalt (III) acetopyruvate, and the like, and organic copper complexes such as copper (II) acetopyruvate. Complexes, organic zinc complexes such as zinc (II) acetamidine pyruvate, organic iron complexes such as iron (III) acetamidine pyruvate, and organic nickel complexes such as nickel (II) acetamidine pyruvate , Organic manganese complexes such as manganese (II) acetamidine pyruvate and the like. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These can be used singly or in combination of two or more kinds. As the metal-based hardening accelerator, an organic cobalt complex is preferably used, and particularly, cobalt (III) acetamidinepyruvic acid is preferably used.

A hardening accelerator can be used individually by 1 type or in combination of 2 or more types. When the content of the hardening accelerator is set to 100% by mass of the nonvolatile matter in the resin composition, it is preferred to use a range of 0.01% to 3% by mass.

-Flame retardant-

Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone-based flame retardant, and a metal hydroxide. The flame retardant can be used alone or in combination of two or more. Although the content of the flame retardant is not particularly limited, when the nonvolatile component in the resin composition is 100% by mass, it is preferably 0.5% to 10% by mass, and more preferably 1% to 9% by mass. Still more preferably, it is 1.5% to 8% by mass.

The resin composition of the present invention is appropriately mixed with the above-mentioned components, and if necessary, it can be kneaded by a mixing means such as a three-roller, a ball mill, a bead mill, a sand mill, or the like by a super-mixer, a planetary mixer, or the like. Or stir to make it as a resin varnish.

Although the application of the resin composition of the present invention is not particularly limited, it can be widely used for sheet-shaped laminated materials such as a film, a prepreg, and a circuit board (such as a laminated board, a multilayer printed circuit board, etc.) and soldering resistance. Etching, underfill material, wafer bonding material, semiconductor sealing material, filling resin, parts embedding resin, etc., are required for the range of applications of the resin composition. Among them, the resin composition of the present invention can be suitably used as a resin composition for an insulating layer of a multilayer printed circuit board, and can be more suitably used as a resin composition for forming a conductor layer by plating (a conductor layer is formed by plating). A resin composition for an insulating layer of a multilayer printed wiring board) or a resin composition for forming a stacked layer of a multilayer printed wiring board. The resin composition of the present invention can also be applied to a circuit board to form an insulating layer in a varnished state, and can also be a film or a prepreg. Used in the form of a laminar laminate.

<Laminar laminate material> (Adhesive film)

Then, the film is formed on a support to form a resin composition layer. The adhesive film can be prepared by a method known to those skilled in the art, such as preparing a resin varnish that dissolves the resin composition in an organic solvent, and applying the resin varnish to a support using a mold coater, etc. It is manufactured by heating or blowing hot air and drying the organic solvent to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol. Acetic esters such as acetate, cellosolve, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, Amidamine-based solvents such as N-methylpyrrolidone and the like. The organic solvent can be used in combination of two or more kinds.

Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is dried so as to be 10% by mass or less, and preferably 5% by mass or less. Although it differs depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, the varnish containing 30 to 60% by mass of the organic solvent can be dried at 50 to 150 ° C for about 3 to 10 minutes. A resin composition layer is formed. This resin composition layer is sometimes referred to as a B-stage film, and is not completely cured, and may be further cured.

The melt viscosity of the resin composition layer at 100 ° C is preferably 35,000 poise or less, more preferably 20,000 poise or less, even more preferably 15000 poise or less, from the viewpoint of obtaining a good laminating or embedding adhesive film. It is preferably below 10,000poise, and particularly preferably below 5000poise. From the viewpoint of preventing immersion during lamination, it is preferably 500 poise or more, more preferably 1000 poise or more, and even more preferably 1500 poise or more. When the resin composition layer is laminated, it is usually carried out at around 100 ° C. Based on the melt viscosity value at 100 ° C, the lamination property of the adhesive film can be evaluated.

The melt viscosity of the resin composition layer of the present invention at 100 ° C. can be measured by a dynamic viscoelasticity method. Specifically, using a parallel plate having a resin content of 1 g and a diameter of 18 mm, the starting temperature was from 60 ° C to 200 ° C, and the measurement conditions were performed at a temperature increase rate of 5 ° C / min, a measurement temperature interval of 2.5 ° C, and a vibration of 1Hz / deg. The dynamic viscoelasticity measurement can measure the melt viscosity of the resin composition layer at 100 ° C. As such a dynamic viscoelasticity measuring device, for example, U.S. B. M type Rheosol-G3000.

The thickness of the resin composition layer formed on the film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer included in the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of thin film formation, it is more preferably 15 to 80 μm, and still more preferably 20 to 50 μm.

Examples of the support include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), and polyethylene naphthalate. Polyester film, poly Various plastic films such as carbonate film and polyimide film. It is also possible to use release paper, metal foils such as copper foil and aluminum foil. Among them, in terms of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. The support and a protective film described later may be subjected to surface treatments such as mud treatment and corona treatment. In addition, the release treatment may be performed using a release agent such as a silicone resin-based release agent, an alkyd resin-based release agent, or a fluororesin-based release agent.

Although the thickness of the support is not particularly limited, it is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more in terms of improving operability. In addition, from the viewpoint of improving cost-effectiveness or efficient digging when digging holes on a support, it is preferably 150 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.

A protective film may be further laminated on the surface on the side opposite to the surface of the support on which the resin composition layer is adhered, depending on the support. In this case, the next film system includes a support, a resin composition layer formed on the support, and a protective film formed on the resin composition layer. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent adhesion or scratches on the surface of the resin composition layer from dust and the like. The film can then be rolled into a roll for storage.

(Prepreg)

The prepreg can be produced by immersing the resin composition of the present invention in a sheet-shaped reinforcing base material by a hot melt method or a solvent method, and heating and semi-hardening it. That is, the resin composition of the present invention can be a prepreg in a state of being immersed in a sheet-like reinforcing substrate. As the sheet-like reinforcing substrate, for example, It is composed of fibers commonly used as fibers for prepregs such as glass cloth and aramid fibers. It is also suitable for forming prepregs on a support.

The hot-melt method does not dissolve the resin composition in an organic solvent, but temporarily coats it on a support, and laminates it on a sheet-shaped reinforcing substrate, or directly coats the sheet-shaped reinforcing substrate by a mold coater. Materials, etc., to make prepregs. Further, the solvent method is performed in the same manner as for the adhesive film, and the resin is dissolved in an organic solvent to prepare a resin varnish, the sheet-shaped reinforcing substrate is impregnated with the varnish, and the resin varnish is impregnated with the sheet-shaped reinforcing substrate, and then dried. Further, the adhesive film may be prepared by performing continuous thermal lamination under heating and pressure conditions from both sides of the sheet-shaped reinforcing substrate. A support, a protective film, etc. can also be used similarly to an adhesive film.

<Multilayer printed circuit board using sheet-like laminated material>

Next, an example of a method for manufacturing a multilayer printed wiring board using the sheet-like laminated material manufactured as described above will be described.

First, a sheet-like laminated material is laminated on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. In addition, the term "circuit board" as used herein refers to a patterned conductor layer (circuit) formed on one or both sides of a substrate as described above. A multilayer printed circuit board in which a conductor layer and an insulating layer are alternately laminated, and one or both sides of the outermost layer of the multilayer printed circuit board are pattern-processed conductor layers (circuits) are also included herein. Circuit board. In addition, the conductor layer table The surface may be roughened in advance by blackening treatment, copper etching, or the like.

When the sheet-like laminated material has a protective film, after removing the protective film, if necessary, the sheet-like laminated material and the circuit board are preheated, and the sheet-like laminated material is laminated while being pressed and heated. In a suitable embodiment, the sheet-shaped laminated material is laminated on the circuit substrate under reduced pressure by a vacuum layer method. Although the lamination conditions are not particularly limited, for example, it is preferable to set the pressing temperature (laminating temperature) to 70 to 140 ° C, and it is preferable to set the pressing pressure (laminating pressure) to 1 to 11 kgf / cm. ² (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m ² ), it is preferable to set the pressing time (lamination time) to 5 to 180 seconds, and it is more preferable to reduce the air pressure below 20mmHg (26.7hPa). Lamination is carried out under pressure. The lamination method may be a batch method or a continuous method using a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, vacuum applicators made by Nichigo Morton, vacuum pressurized laminators made by Meiji Seisakusho, roller dry coaters made by Hitachi Industrial, Hitachi AIC (stock) vacuum laminator.

After laminating a sheet-like laminated material on a circuit board, and after cooling to room temperature, the support is peeled off and the resin composition is thermally cured to form a cured product. Thereby, an insulating layer can be formed on the circuit substrate. Although the conditions for heat curing can be appropriately selected according to the type and content of the resin component in the resin composition, it is preferably selected at 150 ° C to 220 ° C for 20 to 180 minutes, and more preferably at 160 ° C to 210 ° C. 30 ~ 120 minutes range. After forming the insulating layer, if the support is not peeled before curing, it can also be peeled here if necessary.

Further, the sheet-like laminated material may be laminated on one side or both sides of the circuit board using a vacuum press. The lamination step of heating and pressing under reduced pressure can be performed using a general vacuum hot stamping machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The pressing conditions usually set the degree of reduced pressure to 1 × 10 ^-2 MPa or less, and preferably set to a reduced pressure of 1 × 10 ^-3 MPa or less. Although heating and pressurization may be performed in one step, from the viewpoint of regulating resin bleeding, it is preferably performed in two or more steps. For example, it is preferable to perform the first stage of stamping at a temperature of 70 to 150 ° C and a pressure of 1 to 15 kgf / cm ² , and the second stage of stamping at a temperature of 150 to 200 ° C and a pressure of 1 to 40 kgf / cm ² range. The time of each stage is preferably 30 to 120 minutes. In this way, an insulating layer can be formed on the circuit substrate by the thermosetting resin composition layer. Examples of commercially available vacuum hot stamping machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

In the resin composition of the present invention, the average linear thermal expansion coefficient of the cured product from 25 ° C to 150 ° C is preferably 20 ppm or less, more preferably 17 ppm or less, and even more preferably 14 ppm or less. Although the lower limit value is not limited, it is generally 4 ppm or more. The linear thermal expansion rate is measured by using a thermo-mechanical analysis device (Thermo Plus TMA8310) by a thermogravimetric analysis using a tensile weighting method.

In addition, when the sheet-like laminated material of the present invention is laminated on a circuit board and hardened by heat curing, the unevenness (undulation) between the surface of the hardened material on the circuit and the surface other than the circuit is preferably 3 μm or less. . This unevenness can be measured using a non-contact surface roughness meter (Veeco Instruments WYKO NT3300).

Next, a hole is formed in the insulating layer formed on the circuit substrate to form through holes and through holes. The boring process is performed by a known method such as drilling, laser, plasma, and the like, and if necessary, a combination of these methods can be used. Among them, the most common method is a hole digging process using a carbon dioxide gas laser, a YAG laser, or the like. In addition, it is preferable to laminate a sheet-like laminated material on a circuit board, heat-harden a resin composition layer to form an insulating layer, and perform an excavation process on the insulating layer formed on the circuit substrate from a support to form a through hole. In this way, a multilayer printed circuit board is manufactured, and the support is peeled off after the boring process. In this way, by forming a through hole by performing a boring process from the support, the occurrence of stains can be suppressed. In addition, in order to correspond to the reduction in thickness of the multilayer printed circuit board, the top diameter (diameter) of the through hole is preferably 15 to 70 μm, more preferably 20 to 65 μm, and even more preferably 25 to 60 μm.

Next, the surface of the insulating layer is roughened. Examples of the dry roughening treatment include plasma treatment, and examples of the wet roughening treatment include swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution. Sequential method. Although either a dry type or a wet type roughening treatment can be used, a wet type roughening treatment is preferably a point where a concave-convex anchor can be formed on the surface of an insulating layer and a stain in a through hole can be removed. . The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably at 55 to 70 ° C for 8 to 15 minutes). Examples of the swelling liquid include an alkali solution and a surfactant solution, and an alkali solution is preferred. Examples of the alkaline solution include a sodium hydroxide solution and hydroxide Potassium solution and so on. Examples of commercially available swelling liquids include Swelling manufactured by Atotech Japan. Dip. Securiganth P, Swelling. Dip. Securiganth SBU, etc. The roughening treatment by the oxidant is performed by immersing the insulating layer in the oxidant solution at 60 to 80 ° C for 10 to 30 minutes (preferably at 70 to 80 ° C for 15 to 25 minutes). Examples of the oxidant include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved, an aqueous solution of dichromate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid equal to sodium hydroxide. The concentration of the permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidants include Concentrate made by Atotech Japan (stock). Compact CP, Dosing solution SecuriganthP and other alkaline permanganic acid solutions. The neutralization treatment is performed by immersing the insulating layer in the neutralization solution at 30 to 50 ° C for 3 to 10 minutes (preferably, 3 to 8 minutes at 35 to 45 ° C). As the neutralizing solution, an acidic aqueous solution is preferred, and as a commercially available product, a Reduction solution manufactured by Atotech Japan (Stock) is mentioned. Securiganth P.

The Ra (arithmetic average roughness) on the surface of the hardened material of the hardened material of the present invention after roughening treatment is preferably 400 nm or less, more preferably 300 nm or less, and still more preferably 200 nm or less from the point that fine wiring can be formed. Especially preferred is below 100nm. Although the lower limit value is not limited, it is generally 20 nm or more. The arithmetic average roughness (Ra value) of the surface of a hardened | cured material can be measured using a non-contact surface roughness meter. A specific example of the non-contact type surface roughness meter is "WYKO NT3300" manufactured by Veeco Instruments.

Second, the conductor is formed by dry plating or wet plating Layer on the insulating layer. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of the wet plating include a method of forming a conductive layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having a reverse pattern with the conductive layer, and a method of forming a conductive layer only by electroless plating. As a method for subsequent pattern formation, for example, a Subtractive method, a semi-additive method, and the like known to those skilled in the art can be used. Furthermore, by repeating the above-mentioned series of steps several times, a multilayer printed circuit board with multiple layers of stacked layers can be manufactured.

The peeling strength of the plated conductor layer of the cured product of the resin composition of the present invention is preferably 0.4 kgf / cm or more, and more preferably 0.5 kgf / cm or more. Although the upper limit value is not limited, it is generally 1.0 kgf / cm or less. The peeling strength of the plated conductor layer is a conductor layer formed by plating on the surface of the hardened material after the roughening treatment, and the peeling strength of the plated surface of the hardened material and the conductor layer is measured. Examples of the tensile testing machine include "AC-50C-SL" manufactured by TSE.

<Semiconductor device>

A semiconductor device can be manufactured by using the multilayer printed circuit board of the present invention. At the conduction point of the multilayer printed circuit board of the present invention, a semiconductor device can be manufactured by mounting a semiconductor wafer. The so-called "conducting point" refers to "the point of transmitting electrical signals on a multilayer printed circuit board", and its location is not important whether it is a surface or an embedded point. The semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

Semiconductor wafer when manufacturing the semiconductor device of the present invention The mounting method is not particularly limited if the semiconductor wafer can effectively function. Specific examples include a wire bonding mounting method, a flip chip mounting method, and a bumpless stacking layer (BBUL). A mounting method by an anisotropic conductive film (ACF), a mounting method by a non-conductive film (NCF), and the like.

[Example]

Hereinafter, although the present invention will be specifically described by way of examples, the present invention is not limited to these examples. In the following description, unless otherwise stated, "parts" and "%" mean "mass parts" and "mass%", respectively.

<Measurement method. Evaluation method>

First of all, for various determination methods. The evaluation method will be described.

<Evaluation of linear thermal expansion coefficient>

The adhesive films obtained in Examples and Comparative Examples were heated at 190 ° C for 90 minutes to thermally harden the resin composition layer. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile weighting method using a Rigaku thermo mechanical analysis device (Thermo Plus TMA8310). After the test piece was installed in the aforementioned device, the measurement was performed twice under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./minute. In the second measurement, the glass transition temperature and the average linear thermal expansion coefficient from 25 ° C to 150 ° C were calculated.

<Preparation of Arithmetic Mean Roughness (Ra Value) and Peel Strength Measurement Sample> (1) Substrate treatment of inner circuit board

The glass cloth substrate epoxy double-sided copper sheet laminate (the thickness of the copper foil is 18 μm, the thickness of the substrate is 0.3 mm, and R5715ES manufactured by Matsushita Electric Works Co., Ltd.) is used to form the inner layer circuit on the CZ8100 manufactured by MEC 1 μm etching was performed to roughen the copper surface.

(2) Laminating the film

The adhesive films prepared in the examples and comparative examples were laminated on both sides of an inner-layer circuit board using a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.). The lamination system was depressurized for 30 seconds to set the air pressure to 13 hPa or less, and then carried out by pressing at 30 seconds, 100 ° C, and a pressure of 0.74 MPa.

(3) Hardening of resin composition

The laminated adhesive film was cured at 100 ° C. for 30 minutes, and then 180 ° C. for 30 minutes to harden the resin composition to form an insulating layer. The PET film was then peeled.

(4) Roughening

The inner circuit board forming the insulating layer was immersed at 60 ° C. for 10 minutes in Swelling dip containing diethylene glycol monobutyl ether made by Atotech Japan (stock) as a swelling liquid. Securigant P, as a roughening solution, was immersed at 80 ° C for 20 minutes in Concentrate manufactured by Atotech Japan. Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution), as a neutralization solution, immersed at 40 ° C for 5 minutes in a reduction solution made by Atotech Japan. Securiganth P. After drying at 80 ° C for 30 minutes, the surface of the insulating layer after the roughening treatment was measured for arithmetic mean roughness (Ra value) and root mean square roughness (Rq value).

(5) Plating by semi-additive method

In order to form a circuit on the surface of the insulating layer, the inner circuit board was immersed at 40 ° C for 5 minutes in an electroless plating solution containing PdCl ₂ , and then at 25 ° C for 20 minutes in an electroless copper plating solution. After annealing at 150 ° C. for 30 minutes, an etching resistance is formed. After the pattern is formed by etching, copper sulfate electrolytic plating is performed to form a conductor layer having a thickness of 25 μm. Next, annealing was performed at 180 ° C for 30 minutes. This circuit board was measured for peel strength of the plated conductor layer.

<Measurement of arithmetic average roughness (Ra value) after roughening treatment>

Using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments), the Ra value was obtained by using a VSI Contact mode and a 50-fold lens with a measurement range of 121 μm × 92 μm. In addition, an average value of 10 points was obtained as a measurement value.

<Measurement of Peel strength of plated conductor layer>

For the conductor layer of the circuit board, a cut with a width of 10 mm and a length of 100 mm was cut, and this end was peeled off and clamped with a clamp ((strand) D.S.E, Auto com type testing machine AC-50CSL), at room temperature at 50 mm / The speed was measured in minutes at a load (kgf / cm) when 35 mm was peeled in the vertical direction.

<Melting Viscosity Measurement>

The melt viscosity of the resin composition layer of the adhesive film produced in the Example and the comparative example was measured. Use (share) U. B. M-type Rheosol-G3000, using parallel plates with 1g resin volume and 18mm diameter, starting temperature from 60 ° C to 200 ° C, temperature rise rate of 5 ° C / min, measurement temperature interval of 2.5 ° C, and vibration of 1Hz / deg. Determine the melt viscosity.

<Lamination Test>

The adhesive films produced in the examples and comparative examples were laminated on L (wire: wiring width) / S using a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.) with a conductor thickness of 35 μm. (Space: interval width) = 160/160 μm comb-shaped conductor pattern. The lamination was performed by depressurizing for 30 seconds to reduce the air pressure to 13 hPa or less, and then pressing at 30 ° C, 100 ° C, and a pressure of 0.74 MPa. The PET film was peeled from the laminated adhesive film, and the resin composition was cured at a hardening condition of 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to form an insulating layer. The value of the unevenness (Rt: maximum peak-to-valley) between the conductor of the insulating layer and other parts is determined by using a non-contact surface roughness meter (WYKO manufactured by Veeco Instruments) NT3300) was obtained from a VSIContact mode, 10x lens with a measurement range of 1.2mm × 0.91mm. After the lamination, the difference between the unevenness of the conductor and other portions on the conductor was 3.0 μm or less, and was evaluated as ○. After the lamination, the difference between the unevenness of the conductor and other portions on the conductor was greater than 3.0 μm.

[Example 1]

5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.), and biphenylaralkyl type epoxy resin (epoxy equivalent 291, Nippon Kayaku) 8 parts of `` NC3000H '' made by Co., Ltd., 8 parts of naphthol epoxy resin (epoxy equivalent 332, `` ESN-475V '' made by Nippon Steel & Sumitomo Chemical Co., Ltd.), 8 parts of phenoxy resin (made of Japan Epoxy "YX6954BH30" (weight-average molecular weight: 38000) made of resin (stock) is dissolved in 8 parts of a non-volatile resin solution of 30% by mass in a mixed solvent with a mass ratio of 1: 1 of MEK and cyclohexanone, and 8 parts of MEK, 8 parts of cyclohexanone were heated and dissolved while stirring. There are also 26 parts of mixed active ester-based hardener (active group equivalent 223, toluene solution with 65% by mass of non-volatile content, "HPC8000-65T" manufactured by DIC Corporation), and 1-benzyl-2- 1 part of phenylimidazole ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.), spherical silica ("SOC1" manufactured by Admatechs Corporation (with hexamethyldisilazane treatment, average particle diameter 0.25 μm, specific gravity) 2.2 g / m ³ )) 84 parts of those who were surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), from 30 ° C to 150 ° C Spherical glass fillers with an average linear thermal expansion coefficient of 300 ppb / ° C or less ("AZ filler" manufactured by Asahi Glass (average particle size 0.2 μm, specific gravity 2.2 g / m ³ )) with N-phenyl-3-amine group Thirty-six parts of propyltrimethoxysilane (surface-treated by Shin-Etsu Chemical Co., Ltd. "KBM573") were uniformly dispersed with a high-speed rotary mixer to produce a resin varnish. Next, it is coated on a polyethylene terephthalate (thickness: 38 μm, hereinafter referred to as “PET”) in a mold coater so that the thickness of the dried resin composition becomes 40 μm, and the coating is performed at 80 to 120. Dry at 6 ° C (average 100 ° C) for 6 minutes (residual solvent content: about 2% by mass). Next, a 15 μm-thick polypropylene film was rolled onto the surface of the resin composition layer while being rolled into a roll shape. The roll-shaped adhesive film was cut into a width of 507 mm, thereby obtaining a sheet-shaped adhesive film having a size of 507 mm × 336 mm.

[Example 2]

5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.), and biphenylaralkyl type epoxy resin (epoxy equivalent 291, Nippon Kayaku) 8 parts of `` NC3000H '' made by Co., Ltd., 8 parts of naphthol epoxy resin (epoxy equivalent 332, `` ESN-475V '' made by Nippon Steel & Sumitomo Chemical Co., Ltd.), 8 parts of phenoxy resin (made of Japan Epoxy "YX6954BH30" (weight average molecular weight: 38000) made of resin (stock) is dissolved in 8 parts of a non-volatile resin solution (30% by mass of a mixed solvent with a mass ratio of 1: 1 of MEK and cyclohexanone), 10 parts of MEK, While stirring 10 parts of cyclohexanone, it heat-dissolved. There are also 26 parts of mixed active ester-based hardener (active group equivalent 223, toluene solution with 65% by mass of non-volatile content, "HPC8000-65T" manufactured by DIC Corporation), and 1-benzyl-2- 1 part of phenylimidazole ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.), spherical silica ("SOC1" manufactured by Admatechs Corporation (with hexamethyldisilazane treatment, average particle diameter 0.25 μm, specific gravity) 2.2 g / m ³ )) 84 parts of those who were surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), from 30 ° C to 150 ° C Zirconium phosphate-based filler ("ZWP" (average particle diameter: 2.3 μm, broken shape, specific gravity: 3.8 g / m ³ ) made by KCM (strand)) with an average linear thermal expansion coefficient of 300 ppb / ° C or lower. -62 parts of aminopropyltrimethoxysilane (surface-treated by Shin-Etsu Chemical Co., Ltd. ("KBM573")), uniformly dispersed with a high-speed rotary mixer, and a resin varnish was produced. Next, it carried out similarly to Example 1, and obtained the adhesive film.

[Example 3]

5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.), and biphenylaralkyl type epoxy resin (epoxy equivalent 291, Nippon Kayaku) 8 parts of `` NC3000H '' made by Co., Ltd., 8 parts of naphthol epoxy resin (epoxy equivalent 332, `` ESN-475V '' made by Nippon Steel & Sumitomo Chemical Co., Ltd.), 8 parts of phenoxy resin (made of Japan Epoxy "YX6954BH30" (weight average molecular weight: 38000) made of resin (stock) is dissolved in 8 parts of a non-volatile resin solution (30% by mass of a mixed solvent with a mass ratio of 1: 1 of MEK and cyclohexanone), 10 parts of MEK, While stirring 10 parts of cyclohexanone, it heat-dissolved. There are also 26 parts of mixed active ester-based hardener (active group equivalent 223, toluene solution with 65% by mass of non-volatile content, "HPC8000-65T" manufactured by DIC Corporation), and 1-benzyl-2- 1 part of phenylimidazole ("1B2PZ" manufactured by Shikoku Chemical Industries, Ltd.), spherical silica ("SOC1" manufactured by Admatechs Corporation (with hexamethyldisilazane treatment, average particle diameter 0.25 μm, specific gravity) 2.2 g / m ³ )) 84 parts of those who were surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), from 30 ° C to 150 ° C Broken glass filler with an average linear thermal expansion coefficient of 300 ppb / ° C or lower ("DL7400" manufactured by Nippon Electric Glass Co., Ltd. (average particle diameter of 4.8 μm, specific gravity of 2.5 g / m ³ ) with N-phenyl-3-amine 41 parts of propyltrimethoxysilane (surface-treated by Shin-Etsu Chemical Co., Ltd. "KBM573") were uniformly dispersed with a high-speed rotary mixer to produce a resin varnish. Next, it carried out similarly to Example 1, and obtained the adhesive film.

[Example 4]

10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.), and biphenylaralkyl type epoxy resin (epoxy equivalent 291, Nippon Kayaku) 18 parts of `` NC3000H '' made by (stock), 3 parts of naphthalene-type epoxy resin (epoxy equivalent 144, `` EXA4032SS '' made by DIC (stock)), 4 parts of naphthalene-type epoxy resin (epoxy equivalent 162, DIC (stock) 5 parts of "HP-4700"), a phenoxy resin ("YX6954BH30" (weight average molecular weight 38000) manufactured by Japan Epoxy Resin Co., Ltd.) was dissolved in methyl ethyl ketone (hereinafter referred to as "MEK") and 18 parts of a resin solution containing 30% by mass of nonvolatile matter in a mixed solvent having a cyclohexanone mass ratio of 1: 1, and heated and dissolved while stirring 12 parts of MEK and 12 parts of cyclohexanone. There are also 9 parts of mixed naphthol aralkyl-based hardener (215 phenolic hydroxyl equivalent, "SN485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), phenol novolak-based hardener (phenolic hydroxyl equivalent 120, DIC (share MEK solution with a solid content of 60% made by "LA7052") 15 parts, 0.2 parts of 4-dimethylaminopyridine as a hardening accelerator, and spherical silica ("SOC1" (attached by Admatechs) Hexamethysilazane treatment, average particle diameter 0.25 μm, specific gravity 2.2 g / m ³ )) N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") 119 parts of surface treatment, spherical glass filler (average particle diameter 0.2 μm, specific gravity 2.2 g, manufactured by Asahi Glass Co., Ltd. "AZ filler") having an average linear thermal expansion coefficient between 30 ° C and 150 ° C and below 300 ppb / ° C / m ³ )) 51 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) for surface treatment were uniformly dispersed with a high-speed rotary mixer to produce a resin varnish . Next, it carried out similarly to Example 1, and obtained the adhesive film.

[Example 5]

6 parts of liquid bisphenol A-type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.) and naphthol-type epoxy resin (epoxy equivalent 332, Nippon Steel & Sumikin Chemical ( 16 shares of `` ESN-475V ''), 9 parts of naphthalene-type epoxy resin (epoxy equivalent 144, `` EXA4032SS '' by DIC (shares)), 9 parts of naphthalene ether epoxy resin (epoxy equivalent 266, DIC (shares) 6 parts of "EXA7311"), phenoxy resin ("YX6954BH30" (weight average molecular weight 38000) made by Japan Epoxy Resin Co., Ltd.) was dissolved in a mixed solvent with a mass ratio of 1: 1 of MEK and cyclohexanone 5 parts of non-volatile matter 30% by mass of resin solution), and heat-dissolved while stirring in 15 parts of MEK and 15 parts of cyclohexanone. There are also 20 parts of a prepolymer mixed with bisphenol A dicyanate (cyanate equivalent 235, non-volatile content of 75% by mass MEK solution, Lonza Japan (stock) "BA230S75", phenol novolac type multifunctional cyanide 8 parts of ester resin (124 cyanate equivalent, MEK solution with 80% by mass of non-volatile content, "PT30" manufactured by Lonza Japan), active ester hardener (223 equivalent of active group, 65 mass of non-volatile content % Toluene solution, 12 parts of "HPC8000-65T" manufactured by DIC, 0.02 parts of 4-dimethylaminopyridine as a hardening accelerator, and cobalt (III) acetamidine pyruvate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4 parts of a 1% by mass MEK solution, and spherical silica ("SOC1" manufactured by Admatechs Co., Ltd. (with hexamethyldisilazane treatment, average particle diameter of 0.25 μm, specific gravity of 2.2 g / m ³ )) 140 parts of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573"), and the average linear thermal expansion coefficient from 30 ° C to 150 ° C is 300ppb / Spherical glass fillers ("AZ fillers" manufactured by Asahi Glass (average particle size 0.2 μm, specific gravity 2.2 g / m ³ )) below N ° with N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical (stock) system KBM573 ") 60 parts of the surface treatment, and uniformly dispersed with a high-speed rotary mixer to produce resin varnish. Next, it carried out similarly to Example 1, and obtained the adhesive film.

[Example 6]

5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.), and biphenylaralkyl type epoxy resin (epoxy equivalent 291, Nippon Kayaku) 8 parts of `` NC3000H '' made by Co., Ltd., 8 parts of naphthol epoxy resin (epoxy equivalent 332, `` ESN-475V '' made by Nippon Steel & Sumitomo Chemical Co., Ltd.), 8 parts of phenoxy resin (made of Japan Epoxy "YX6954BH30" (weight-average molecular weight: 38000) made of resin (stock) is dissolved in 8 parts of a non-volatile resin solution of 30% by mass in a mixed solvent with a mass ratio of 1: 1 of MEK and cyclohexanone, and 8 parts of MEK, 8 parts of cyclohexanone were heated and dissolved while stirring. There are also 26 parts of mixed active ester-based hardener (active group equivalent 223, toluene solution with 65% by mass of non-volatile content, "HPC8000-65T" manufactured by DIC Corporation), and 1-benzyl-2- 1 part of phenylimidazole ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.), a spherical glass filler (average linear thermal expansion coefficient from 30 ° C to 150 ° C) of 300 ppb / ° C or less ("Asahi Glass Co., Ltd.""AZfiller" (average particle size 0.2 μm, specific gravity 2.2 g / m ³ )) Surface treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 105 It is uniformly dispersed with a high-speed rotary mixer to produce a resin varnish. Next, it carried out similarly to Example 1, and obtained the adhesive film.

[Comparative Example 1]

5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.), and biphenylaralkyl type epoxy resin (epoxy equivalent 291, Nippon Kayaku) 8 parts of `` NC3000H '' made by Co., Ltd., 8 parts of naphthol epoxy resin (epoxy equivalent 332, `` ESN-475V '' made by Nippon Steel & Sumitomo Chemical Co., Ltd.), 8 parts of phenoxy resin (made of Japan Epoxy "YX6954BH30" (weight-average molecular weight: 38000) made of resin (stock) is dissolved in 8 parts of a non-volatile resin solution of 30% by mass in a mixed solvent with a mass ratio of 1: 1 of MEK and cyclohexanone, while 12 parts of MEK, While stirring 12 parts of cyclohexanone, it heat-dissolved. There are also 26 parts of mixed active ester-based hardener (active group equivalent 223, toluene solution with 65% by mass of non-volatile content, "HPC8000-65T" manufactured by DIC Corporation), and 1-benzyl-2- 1 part of phenylimidazole ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd.), spherical silica ("SOC1" manufactured by Admatechs Corporation (with hexamethyldisilazane treatment, average particle diameter 0.25 μm, specific gravity) 2.2 g / m ³ )) 150 parts of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., "KBM573") for surface treatment, uniformly dispersed with a high-speed rotary mixer, Make resin varnish. Next, it carried out similarly to Example 1, and obtained the adhesive film.

[Table 1]

From this result, it is clear that the resin composition of the present invention provides a resin composition which has a low linear thermal expansion rate and a low roughness, but is a hardened product having a high peeling strength, and can have excellent lamination properties. Sheet-like laminate.

Claims (20)

A resin composition comprising (A) an epoxy resin, (B) a hardener, (C) a filler having an average linear thermal expansion coefficient of 300 ppb / ° C from 30 ° C to 150 ° C, and (C) from 30 Filler-based glass fillers having an average linear thermal expansion coefficient of 300 ppb / ° C or lower between 150 ° C and 150 ° C, and when the non-volatile content in the resin composition is set to 100% by volume, the content of (C) is 5 to 80% A filler having an average linear thermal expansion coefficient between 30 ° C and 150 ° C of 300 ppb / ° C or lower. For example, the resin composition of claim 1, wherein when the non-volatile content in the resin composition is set to 100% by volume, the average linear thermal expansion coefficient of (C) from 30 to 150 ° C is included in the range of 10 to 80% by volume. Fillers below 300 ppb / ° C. For example, the resin composition of claim 1, wherein (C) the filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C of 300 ppb / ° C or less has an average particle diameter of 0.01 to 10 µm. For example, the resin composition of claim 1, wherein the specific gravity of the filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C of 300 ppb / ° C or lower is 1 to 7 g / cm ³ . The resin composition according to claim 1, wherein the filler having an average linear thermal expansion coefficient of (C) from 30 ° C to 150 ° C of 300 ppb / ° C or less is spherical or broken. The resin composition according to claim 1, wherein (C) the filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C of 300 ppb / ° C or lower is a titanium-doped glass filler. For example, the resin composition of claim 1, further comprising (C) a filler other than a filler having an average linear thermal expansion coefficient from 300 ° C to 150 ° C of 300 ppb / ° C or less, and setting a nonvolatile component in the resin composition When it is 100% by volume, the total filler content is 40 to 80% by volume. The resin composition according to claim 1, wherein (B) the curing agent is one or more selected from the group consisting of an active ester curing agent, a cyanate ester curing agent, a phenol curing agent, and a naphthol curing agent. The resin composition according to claim 1, wherein (A) the epoxy resin is a bisphenol A epoxy resin, a biphenylaralkyl epoxy resin, a naphthol epoxy resin, a naphthalene epoxy resin, or naphthalene Ether-type epoxy resin, or a mixture of two or more of these, (B) a hardener-based active ester-based hardener, and (C) an average linear thermal expansion coefficient of 300 ppb / ° C from 30 ° C to 150 ° C The filler is a doped titanium type glass filler. For example, the resin composition of claim 1, wherein the average linear thermal expansion coefficient of the hardened material of the resin composition from 25 ° C to 150 ° C is 20 ppm or less, and the hardened surface of the hardened material of the resin composition is roughened. Ra is 400 nm or less, and a hardened body of the resin composition is formed. A conductive layer is formed by plating on the hardened surface of the hardened body after roughening treatment, and the peeling strength of the hardened surface and the conductive layer is plated. It is 0.4 kgf / cm or more. The resin composition according to claim 1, which is used for an insulating layer of a multilayer printed circuit board. An adhesive film comprising the resin composition according to any one of claims 1 to 11. For example, the adhesive film of claim 12, wherein the resin composition layer of the adhesive film has a melt viscosity at 100 ° C of 35,000 poise or less. A cured product, which is a resin composition according to any one of claims 1 to 11. The cured product according to claim 14, wherein the average linear thermal expansion coefficient from 25 ° C to 150 ° C is 20 ppm or less. The hardened product according to claim 14, wherein Ra of the surface of the hardened product after the roughening treatment is 400 nm or less. The hardened product according to claim 14, wherein when the conductor layer is formed by plating on the surface of the hardened object after the roughening treatment of the hardened object, the plating peel strength of the hardened surface and the conductor layer is 0.4 kgf / cm or more. . A multilayer printed circuit board having a hardened body as claimed in claim 14. A semiconductor device characterized by using a multilayer printed circuit board as claimed in claim 18. A resin composition for an insulating layer of a multilayer printed circuit board, comprising (A) an epoxy resin, (B) a hardener, and (C) an average linear thermal expansion coefficient from 30 ° C to 150 ° C of 300 ppb / ° C or less The resin composition for an insulating layer of a multilayer printed circuit board of a filler is characterized in that the (A) epoxy resin is a bisphenol A type epoxy resin, a biphenylaralkyl type epoxy resin, and a naphthol type epoxy resin. Resin, naphthalene-type epoxy resin, naphthalene ether-type epoxy resin, or a mixture of two or more of these, the (B) hardener is an active ester-based hardener, and the (C) is between 30 ° C and 150 ° C. The filler is a doped titanium-type glass filler having an average linear thermal expansion coefficient of 300 ppb / ° C or lower. The average linear thermal expansion coefficient of the hardened body of the resin composition from 25 ° C to 150 ° C is 20 ppm or lower. The hardened body of the resin composition Ra of the surface of the hardened material after the roughening treatment is 400 nm or less, and a hardened material of the resin composition is formed. A conductive layer is formed on the surface of the hardened material after the roughening treatment of the hardened material by plating, and the surface of the hardened material The plating peeling strength with this conductor layer is 0.4 kgf / cm or more.