JP6801736B2 - Resin composition, adhesive film, cured product, multilayer printed wiring board and semiconductor device - Google Patents

Description

The present invention relates to a resin composition.

Multi-layer printed wiring boards are widely used in various electronic devices and electronic components. As a manufacturing technique for a multilayer printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer circuit board provided with a circuit conductor is known.

The manufacturing method by the build-up method is generally carried out by the following procedure. First, a resin composition layer is provided on an inner circuit board, and the resin composition layer is cured 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 fine irregularities on the surface of the insulating layer. Then, a conductor layer having a predetermined 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 wiring board, in order to prevent delamination and wiring breakage due to the difference in thermal expansion between the insulating layer and the conductor layer, the interlayer insulating material is required to have a low coefficient of linear thermal expansion. It is known that the resin composition used for forming the insulating layer is highly filled with a filler to increase the coefficient of linear thermal expansion (for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2005-38821 Japanese Unexamined Patent Publication No. 2006-4854

As a result of studying with a conventional filler, the present inventors have found that as the filling amount increases, the melt viscosity and the surface roughness increase, and it tends to be difficult to form fine wiring.
An object of the present invention is to provide a resin composition that provides a cured product having a low coefficient of linear thermal expansion, low roughness and high peel strength, and a sheet-like laminated material having excellent laminating properties.

As a result of diligent studies in view of the above problems, the present inventors have found that (A) an epoxy resin, (B) a curing agent, and (C) an average coefficient of linear thermal expansion between 30 ° C. and 150 ° C. is 300 ppb. It has been found that the above problems can be solved by using a resin composition containing a filler of / ° C. or lower, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a filler having an average linear thermal expansion coefficient of 300 ppb / ° C or less between 30 ° C. and 150 ° C.
[2] When the non-volatile component in the resin composition is 100% by volume, (C) contains 5 to 80% by volume of a filler having an average linear thermal expansion coefficient of 300 ppb / ° C. or less between 30 ° C. and 150 ° C. , [1].
[3] (C) The average particle size of a filler having an average coefficient of linear thermal expansion between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less is 0.01 to 10 μm, according to [1] or [2]. Resin composition.
[4] (C) Any of [1] to [3], wherein the specific gravity of the filler having an average linear thermal expansion coefficient of 300 ppb / ° C or less between 30 ° C. and 150 ° C. is 1 to 7 g / cm ³ . The resin composition described.
[5] (C) Any of [1] to [4], wherein the filler having an average linear thermal expansion coefficient of 300 ppb / ° C or less between 30 ° C. and 150 ° C. is a spherical inorganic filler or a crushed inorganic filler. The resin composition described.
[6] (C) A filler having an average linear thermal expansion coefficient of 300 ppb / ° C. or less between 30 ° C. and 150 ° C. is at least one selected from a glass filler and a zirconium phosphate-based filler. [1] ] To [5].
[7] (C) The filler according to any one of [1] to [6], wherein the filler having an average linear thermal expansion coefficient of 300 ppb / ° C or less between 30 ° C. and 150 ° C. is a titanium-doped glass filler. Resin composition.
[8] (B) Any one of [1] to [7], wherein the curing agent is at least one selected from an active ester-based curing agent, a cyanate ester-based curing agent, a phenol-based curing agent, and a naphthol-based curing agent. The resin composition described.
[9] (A) The epoxy resin is a bisphenol A type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a naphthylene ether type epoxy resin, or a mixture of two or more thereof.
(B) The curing agent is an active ester-based curing agent.
(C) The resin composition according to any one of [1] to [8], wherein the filler having an average linear thermal expansion coefficient of 300 ppb / ° C. or less between 30 ° C. and 150 ° C. is a titanium-doped glass filler. ..
[10] The average linear thermal expansion coefficient of the cured product of the resin composition from 25 ° C. to 150 ° C. is 20 ppm or less.
The Ra of the surface of the cured product after the roughening treatment in the cured product of the resin composition is 400 nm or less, and the cured product of the resin composition is formed on the surface of the cured product after the roughening treatment of the cured product. The resin composition according to any one of [1] to [9], wherein a conductor layer is formed by plating, and the plating peel strength between the cured product 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 wiring board.
[12] An adhesive film containing the resin composition according to any one of [1] to [11].
[13] The adhesive film according to [12], wherein the resin composition layer of the adhesive film has a melt viscosity of 35,000 poise or less at 100 ° C.
[14] A cured product of the 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 cured product according to [14] or [15], wherein the Ra on the surface of the cured product after the roughening treatment is 400 nm or less.
[17] When a conductor layer is formed by plating on the surface of the cured product after the roughening treatment of the cured product, the plating peel strength between the surface of the cured product and the conductor layer is 0.4 kgf / cm or more [14]. The cured product according to any one of [16].
[18] A multilayer printed wiring board having the cured product according to any one of [14] to [17].
[19] A semiconductor device characterized by using the multilayer printed wiring board according to [18].
[20] For an insulating layer of a multilayer printed wiring board containing (A) an epoxy resin, (B) a curing agent, and (C) a filler having an average linear thermal expansion coefficient of 300 ppb / ° C or less between 30 ° C. and 150 ° C. It is a resin composition
The (A) epoxy resin is a bisphenol A type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a naphthylene ether type epoxy resin, or a mixture of two or more thereof.
The (B) curing agent is an active ester-based curing agent.
The filler having an average linear thermal expansion coefficient of 300 ppb / ° C. or less between (C) 30 ° C. and 150 ° C. is a titanium-doped glass filler.
The average linear thermal expansion coefficient of the cured product of the resin composition from 25 ° C. to 150 ° C. is 20 ppm or less.
The Ra of the surface of the cured product after the roughening treatment in the cured product of the resin composition is 400 nm or less, and the cured product of the resin composition is formed on the surface of the cured product after the roughening treatment of the cured product. A resin composition for an insulating layer of a multilayer printed wiring board, wherein a conductor layer is formed by plating, and the plating peel strength between the cured product surface and the conductor layer is 0.4 kgf / cm or more.

According to the present invention, it is possible to provide a cured product having a low coefficient of thermal expansion and a low roughness but having a high peel strength, and a resin composition that provides a sheet-like laminated material having excellent laminating properties.

The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) a filler having an average coefficient of linear thermal expansion of 300 ppb / ° C or less between 30 ° C. and 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, dicyclopentadiene type epoxy resin, and trisphenol epoxy resin. , Naftor novolac epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthalene tetrafunctional epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, Glysidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, complex Examples thereof include a ring type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, and a trimethylol type epoxy resin. Of these, bisphenol A type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, and a mixture of two or more thereof are preferable. One type of epoxy resin may be used alone, or two or more types may be used in combination.

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

Further, it is preferable to contain a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "liquid epoxy resin") and a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "solid epoxy resin"). .. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the insulating layer formed by curing the resin composition is also improved.

As the liquid epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a naphthalene type epoxy resin is preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a naphthalene type epoxy resin is preferable. More preferred. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "EXA4032SS", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., and "jER828EL" (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "ZX1059" (bisphenol A type epoxy resin and bisphenol F type epoxy) manufactured by Nippon Steel Chemical Co., Ltd. A mixture of resins) and the like. As the liquid epoxy resin, "HP4032SS" (naphthalene type epoxy resin) and "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) are particularly preferable. The liquid epoxy resin may be used alone or in combination of two or more.

Examples of the solid epoxy resin include tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin. Preferably, a tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferable, and a biphenyl type epoxy resin is further preferable. Specific examples of the solid epoxy resin include "HP-4700", "HP-4710" (tetrafunctional naphthalene type epoxy resin), "N-690" (cresol novolac type epoxy resin), and "cresol novolac type epoxy resin" manufactured by DIC Co., Ltd. "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP7200H", "HP7200K-65I" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4" , "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000" , "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical ( Examples thereof include "YX4000H", "YL6121" (biphenyl type epoxy resin) and "YX4000HK" (bixilenol type epoxy resin) manufactured by Co., Ltd. In particular, "YX4000HK" (bixylenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC3000L" (biphenyl type epoxy resin), and "HP7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation are preferable. .. The solid epoxy resin may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 4 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) appropriate adhesiveness is provided when used in the form of an adhesive film, and ii) when used in the form of an adhesive film. Sufficient flexibility can be obtained, handleability is improved, and iii) an insulating layer having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is 1: 0.3 to 1: 3.5 in terms of mass ratio. Is more preferable, the range of 1: 0.6 to 1: 3 is further preferable, and the range of 1: 0.8 to 1: 2.5 is particularly preferable.

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

The epoxy equivalent of the epoxy resin is preferably 50 to 3000, more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having low surface roughness is provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

<(B) Hardener>
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include an active ester-based curing agent, a cyanate ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, and a benzoxazine-based curing agent. Can be mentioned. Among them, it is preferable to use one or more selected from an active ester-based curing agent, a cyanate ester-based curing agent, a phenol-based curing agent, and a naphthol-based curing agent, and an active ester-based curing agent is more preferable. The curing agent may be used alone or in combination of two or more.

The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. The active ester-based curing agent 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. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based 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, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadienyldiphenol, and phenol novolac.

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 acetylated product of phenol novolac, and an active ester compound containing a benzoyl product of phenol novolac are preferable. Of these, an active ester compound containing a dicyclopentadiene-type diphenol condensed structure is more preferable.

Specific examples of the active ester curing agent containing a dicyclopentadiene-type diphenol condensation structure include a compound represented by the following formula (1).

In the formula (1), the two Rs are phenyl groups or naphthyl groups independently of each other. k represents 0 or 1. n is an average of 0.05 to 2.5 in repeating units.

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

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene-type diphenol condensation structure. (Manufactured by), "EXB9416-70BK" (manufactured by DIC Co., Ltd.) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac, and phenol novolac. Examples of the active ester compound containing a benzoyl compound include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4, 4'-Etilidendidiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolak and the like, and prepolymers in which these cyanate resins are partially triazined. Preferred specific examples of the cyanate ester-based curing agent are "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins) and "BA230" (a part of bisphenol A disocyanate) manufactured by Lonza Japan Co., Ltd. Prepolymers, which are all triazinized to form a trimer) and the like.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance. Further, from the viewpoint of adhesion to the conductor layer (circuit wiring), a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, it is preferable to use a triazine skeleton-containing phenol novolac resin as a curing agent from the viewpoint of heat resistance and adhesion to the conductor layer (peeling strength).

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" manufactured by Toto Kasei Co., Ltd. , DIC Corporation's "LA7052", "LA7054", "LA3018" and the like.

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

The amount of the curing agent in the resin composition is not particularly limited as long as the epoxy resin can be cured, but when the non-volatile component in the resin composition is 100% by mass, for example, 15 to 50% by mass, preferably 20 to 45% by mass. %, More preferably 25-40% by mass.

<(C) Filler with an average coefficient of linear thermal expansion of 300 ppb / ° C or less between 30 ° C and 150 ° C>
As a method for measuring the average coefficient of linear thermal expansion of the filler between 30 ° C. and 150 ° C., for example, a known method such as a thermal expansion meter for detecting the elongation of the sample with a laser interferometer or an X-ray diffraction method is used. be able to.
As the "filler having an average coefficient of linear thermal expansion of 300 ppb / ° C or less between 30 ° C. and 150 ° C.", an inorganic filler having an average coefficient of linear thermal expansion of 300 ppb / ° C. or less between 30 ° C. and 150 ° C. Is preferable, and spherical inorganic fillers and crushed inorganic fillers having an average coefficient of linear thermal expansion of 300 ppb / ° C or less between 30 ° C. and 150 ° C. are more preferable, and average linear thermal expansion between 30 ° C. and 150 ° C. A spherical inorganic filler having a ratio of 300 ppb / ° C. or less is more preferable. As a specific example, a glass filler, a zirconium phosphate-based filler, a cordierite-based filler, a silicon oxide-based filler, and a tungsten acid having an average coefficient of linear thermal expansion between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less. Examples thereof include zirconium-based fillers and manganese nitride-based fillers. Among them, it is preferable to use one or more selected from a glass filler and a zirconium phosphate-based filler from the viewpoints that the cured product can have a low roughness and the melt viscosity of the adhesive film can be lowered. As the glass filler, a titanium-doped glass filler is preferable, and a titanium-doped spherical glass filler is more preferable.

As the titanium-doped glass filler, for _example, TiCl ₄ and SiCl ₄ as glass-forming raw material for TiO 2 -SiO ₂ glass, was mixed after each is gasified, heat hydrolysis in an oxyhydrogen flame (flame hydrolysis There are TiO _2- SiO ₂ glass fine particles obtained by disassembling). Such a titanium-doped glass filler can be produced by the method described in International Publication No. 2010/134449, and as an example of a commercially available product, "AZ filler" (linear thermal expansion) manufactured by Asahi Glass Co., Ltd. Rate (average value at 30-150 ° C.): 0.2 ppm / ° C. titanium-doped spherical glass filler). Examples of commercially available zirconium phosphate-based fillers include "ZWP" (linear thermal expansion coefficient (average value at 30-150 ° C.): -0.3 ppm / ° C.) manufactured by KCM Corporation. Examples of commercially available crushed glass fillers include "DL7400" manufactured by Nippon Electric Glass Co., Ltd. (linear thermal expansion coefficient (average value of 30-150 ° C.): -1.1 ppm / ° C.).

(C) The average particle size of the filler having an average linear thermal expansion coefficient of 300 ppb / ° C. or less between 30 ° C. and 150 ° C. is such that the cured product has low roughness and fine wiring can be formed, and the resin composition. From the viewpoint of increasing the fluidity and improving the laminateability, the range of 0.01 μm to 10 μm is preferable, the range of 0.05 μm to 8 μm is more preferable, the range of 0.1 μm to 5 μm is further preferable, and the range of 0.2 μm to 0.2 μm. The range of 3 μm is even more preferable. The average particle size of the filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, one in which the filler is dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, LA-500 manufactured by HORIBA, Ltd. or the like can be used.

(C) The specific gravity of the filler having an average coefficient of linear thermal expansion of 300 ppb / ° C or less between 30 ° C. and 150 ° C. is 1 g / cm ^{3 to} 7 g from the viewpoint of preventing separation of varnish and uniformity of composition in the film. / range cm ³ are ^preferred, more preferably in the range of 1 g / cm 3 to 5 g / cm ^3, a range of 1.5 g ^/ cm 3 to 3 g / cm ³ is more preferred.

(C) The content of the filler having an average linear thermal expansion coefficient of 300 ppb / ° C or less between 30 ° C. and 150 ° C. is the low thermal expansion of the cured product when the non-volatile component in the resin composition is 100% by volume. From the viewpoint of conversion, 5% by volume or more is preferable, 10% by volume or more is more preferable, and 15% by volume or more is further preferable. Further, from the viewpoint of the fluidity of the resin composition, 80% by volume or less is preferable, 70% by volume or less is more preferable, and 65% by volume or less is further preferable.

In the resin composition of the present invention, as long as the effect of the present invention is exhibited, (C) with a filler having an average coefficient of linear thermal expansion between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less, if necessary. It may contain other fillers.

As a filler other than the filler having an average linear thermal expansion coefficient of 300 ppb / ° C or less between 30 ° C. and 150 ° C., for example, an average linear thermal expansion coefficient of more than 300 ppb / ° C. between 30 ° C. and 150 ° C. Silica, 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, titanic acid Examples thereof include calcium, magnesium titanate, bismuth titanate, titanium oxide, barium titanate, and calcium zirconate. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica are particularly suitable. Further, as silica, spherical silica is preferable. One type of filler may be used alone, or two or more types may be used in combination. As commercially available spherical fused silica, "SOC2" (average coefficient of linear thermal expansion between 30 ° C. and 150 ° C.) and "SOC1" (30 ° C. to 150 ° C.) manufactured by Admatex Co., Ltd. Average coefficient of linear thermal expansion up to ° C .: 0.5 ppm / ° C).

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

The content of all fillers in the resin composition of the present invention (total content of fillers having an average linear thermal expansion coefficient of 300 ppb / ° C or less between 30 ° C. and 150 ° C. and other fillers) is determined. When the non-volatile component in the resin composition is 100% by volume, it is preferably 40% by volume or more, more preferably 50% by volume or more, from the viewpoint of low thermal expansion of the cured product. Further, from the viewpoint of fluidity at the time of laminating the resin composition, 80% by volume or less is preferable, 70% by volume or less is more preferable, and 65% by volume or less is further preferable.

In order to improve moisture resistance and dispersibility, the above fillers include silane coupling agents (epoxysilane-based coupling agents, aminosilane-based coupling agents, mercaptosilane-based coupling agents, etc.), titanate-based coupling agents, silazane compounds, etc. It is preferable that the surface is treated with the surface treatment agent of. These may be used alone or in combination of two or more.

Examples of the epoxysilane-based coupling agent include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, and (3,4-epoxycyclohexyl). Examples thereof include ethyltrimethoxysilane, and examples of the aminosilane-based coupling agent include aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N- (2-aminoethyl). Examples thereof include aminopropyltrimethoxysilane, and examples of the mercaptosilane-based coupling agent include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane. These may be used alone or in combination of two or more. Examples of commercially available coupling agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. ), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The resin composition of the present invention may further contain the following other components, such as additives such as a thermoplastic resin, a curing accelerator and a flame retardant.

-Thermoplastic resin-
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide-imide resin, polyether sulfone resin, polysulfone resin and the like. The thermoplastic resin may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin 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 polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K- by Showa Denko Corporation as a column. 804L / K-804L can be measured using chloroform or the like as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen Examples thereof include a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" manufactured by Mitsubishi Chemical Corporation. Bisphenol acetophenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Toto Kasei Co., Ltd., "YL7553", "YL6794", "YL7213" and "YL7213" manufactured by Mitsubishi Chemical Corporation. Examples thereof include "YL7290" and "YL7482".

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

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by New Japan Chemical Co., Ltd. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (described in JP-A-2002-12667 and JP-A-2000-319386).

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

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

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

The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass, assuming that the non-volatile component in the resin composition is 100% by mass. More preferably, it is by mass. By setting the content of the thermoplastic resin in such a range, the viscosity of the resin composition becomes appropriate, and a resin composition having a uniform thickness and bulk properties can be formed.

-Curing accelerator-
Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, amine-based curing accelerators, and imidazole-based curing agents. Curing accelerators and metal-based curing accelerators are preferable.

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

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo [. 5.4.0] -undecene and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo [5.4.0] -undecene are preferable.

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

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

The metal-based curing accelerator is not particularly limited, and examples thereof include an organometallic complex or an organometallic salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include an organic zinc complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like. These may be used alone or in combination of two or more. As the metal-based curing accelerator, it is preferable to use an organic cobalt complex, and in particular, cobalt (III) acetylacetonate is preferably used.

The curing accelerator may be used alone or in combination of two or more. The content of the curing accelerator is preferably in the range of 0.01% by mass to 3% by mass when the non-volatile component in the resin composition is 100% by mass.

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

The resin composition of the present invention appropriately mixes the above components, and if necessary, kneads or stirs by a kneading means such as a three-roll, ball mill, bead mill, sand mill, or a stirring means such as a super mixer or a planetary mixer. By doing so, it can be produced as a resin varnish.

The use of the resin composition of the present invention is not particularly limited, but is limited to adhesive films, sheet-like laminated materials such as prepregs, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, and die bonding. It can be used in a wide range of applications in which a resin composition is required, such as materials, semiconductor encapsulants, hole-filling resins, and component-filling resins. 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 wiring board, and is a resin composition for forming a conductor layer by plating (a conductor layer is formed by plating). It can be more preferably used as a resin composition for an insulating layer of a multilayer printed wiring board) or a resin composition for forming a build-up layer of a multilayer printed wiring board. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, or can be used in the form of a sheet-like laminated material such as an adhesive film or a prepreg.

<Sheet-like laminated material>
(Adhesive film)
The adhesive film has a resin composition layer formed on the support. For the adhesive film, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared by a method known to those skilled in the art, and the resin varnish is applied to a support using a die coater or the like, and further heated. Alternatively, it can be produced by drying the organic solvent by blowing hot air or the like 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, and carbitol such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, 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 resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, for example, the resin composition layer is formed by drying the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do. This resin composition layer is sometimes called a B-stage film, and is not completely cured, so that curing can proceed further.

The melt viscosity of this resin composition layer at 100 ° C. is preferably 35,000 poise or less, more preferably 20,000 poise or less, and 15,000 poise or less from the viewpoint of obtaining an adhesive film having good laminateability and embedding property. Is even more preferably 10,000 poise or less, and from the viewpoint of suppressing the difference in unevenness on the surface of the insulating layer and improving the fine wiring formability, it is 8000 poise or less, 7000 poise or less, 6000 poise or less, or 5000 poise or less. Especially preferable. Further, from the viewpoint of preventing oozing during laminating, 500 poise or more is preferable, 1000 poise or more is more preferable, and 1500 poise or more is further preferable. Since the resin composition layer is usually laminated at around 100 ° C., the laminating property of the adhesive film can be evaluated from the melt viscosity value at 100 ° C.

The melt viscosity of the resin composition layer of the present invention at 100 ° C. can be measured by a dynamic viscoelastic method. Specifically, using a parallel plate having a resin amount of 1 g and a diameter of 18 mm, measurement conditions of a starting temperature of 60 ° C. to 200 ° C., a heating rate of 5 ° C./min, a measurement temperature interval of 2.5 ° C., and a vibration of 1 Hz / deg. By performing the dynamic viscoelasticity measurement at 100 ° C., the melt viscosity of the resin composition layer at 100 ° C. can be measured. Examples of such a dynamic viscoelasticity measuring device include a model Rheosol-G3000 manufactured by UBM Co., Ltd.

The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater 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 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of thinning, 15 to 80 μm is more preferable, and 20 to 50 μm is further preferable.

Examples of the support include a polyolefin film such as polyethylene, polypropylene, and polyvinyl chloride, a polyester film such as polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), a polyethylene naphthalate, a polycarbonate film, and a polyimide film. Various plastic films can be mentioned. Further, a paper pattern, a copper foil, a metal foil such as an aluminum foil, or the like may be used. Among them, a plastic film is preferable, and a polyethylene terephthalate film is more preferable from the viewpoint of versatility. The support and the protective film described later may be subjected to surface treatment such as mud treatment and corona treatment. Further, the mold release treatment may be performed with a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, or a fluororesin-based mold release agent.

The thickness of the support is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more in terms of improving handleability. Further, from the viewpoint of improving cost performance and being able to perform efficient drilling when drilling from above the support, 150 μm or less is preferable, 100 μm or less is more preferable, and 50 μm or less is further preferable.

A protective film similar to the support can be further laminated on the surface of the resin composition layer opposite to the surface in which the support is in close contact. In this case, the adhesive film 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 dust and the like from adhering to the surface of the resin composition layer and scratches. The adhesive film can also be rolled up and stored.

(Prepreg)
The prepreg can be produced by impregnating a sheet-shaped 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 prepreg. That is, it can be a prepreg in which the resin composition of the present invention is impregnated in the sheet-shaped reinforcing base material. As the sheet-shaped reinforcing base material, for example, those made of fibers commonly used as prepreg fibers such as glass cloth and aramid fibers can be used. A prepreg formed on the support is preferable.

In the hot melt method, the resin composition is once coated on the support without being dissolved in an organic solvent and then laminated on the sheet-shaped reinforcing base material, or directly coated on the sheet-shaped reinforcing base material by a die coater. This is a method of manufacturing a prepreg. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as an adhesive film, a sheet-shaped reinforcing base material is immersed in the varnish, and the sheet-shaped reinforcing base material is impregnated with the resin varnish. It is a method of drying. It can also be prepared by continuously heat laminating the adhesive film from both sides of the sheet-shaped reinforcing base material under heating and pressure conditions. A support, a protective film, or the like can be used in the same manner as the adhesive film.

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

First, the sheet-shaped laminated material is laminated (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 substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. Here, the circuit board means a circuit board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. Further, in a multi-layer printed wiring board in which conductor layers and insulating layers are alternately laminated, one or both sides of the outermost layer of the multi-layer printed wiring board is a conductor layer (circuit) in which a pattern is processed. It is included in the circuit board mentioned above. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching or the like.

When the sheet-shaped laminated material has a protective film, after removing the protective film, the sheet-shaped laminated material and the circuit board are preheated as necessary, and the sheet-shaped laminated material is pressurized and heated. Laminate on the circuit board. In one preferred embodiment, the sheet-like laminated material is laminated to a circuit board under reduced pressure by a vacuum laminating method. The laminating conditions are not particularly limited, but for example, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C., and the crimping pressure (lamination pressure) is preferably 1 to 11 kgf / cm ² (9.8 ×). 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the crimping time (lamination time) is preferably 5 to 180 seconds, and the lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the laminating method may be a batch method or a continuous method using a roll. Vacuum laminating can be done using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum applicators manufactured by Nichigo Morton Co., Ltd., vacuum pressurized laminators manufactured by Meiki Seisakusho Co., Ltd., roll-type dry coaters manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Vacuum laminator and the like can be mentioned.

After laminating the sheet-like laminated material on the circuit board, it is cooled to around room temperature, and then the support is peeled off when peeled off, and the resin composition is thermoset to form a cured product. As a result, an insulating layer can be formed on the circuit board. The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150 ° C. to 220 ° C. for 20 to 180 minutes, more preferably 160 ° C. to 210 ° C. Is selected in the range of 30 to 120 minutes. If the support is not peeled off after the insulating layer is formed and before curing, it can be peeled off here if necessary.

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

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, preferably 17 ppm or less, and even more preferably 14 ppm or less. There is no limit to the lower limit, but it is generally 4 ppm or more. The coefficient of linear thermal expansion can be measured by performing thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer (Thermo Plus TMA8310) manufactured by Rigaku Co., Ltd.

Further, when the sheet-like laminated material of the present invention is laminated on a circuit board and a cured product is prepared by thermosetting, the difference in unevenness (undulation) between the surface of the cured product on the circuit and the surface other than the circuit is determined. It is preferably 3 μm or less. This unevenness difference can be measured using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Sturments).

Next, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. The drilling process can be performed by, for example, a known method such as a drill, a laser, or plasma, and if necessary, a combination of these methods. Among them, the most common method is drilling with a laser such as a carbon dioxide laser or a YAG laser. Further, the sheet-like laminated material is laminated on the circuit board, the resin composition layer is thermoset to form an insulating layer, and the insulating layer formed on the circuit board is drilled from above the support to form a via hole. Therefore, it is preferable to manufacture a multilayer printed wiring board, and it is preferable to peel off the support after drilling. In this way, the occurrence of smear can be suppressed by forming a via hole by drilling a hole from above the support. Further, in order to cope with the thinning of the multilayer printed wiring board, the top diameter (diameter) of the via hole is preferably 15 to 70 μm, more preferably 20 to 65 μm, and further 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 a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Either dry or wet roughening treatment may be adopted, but the wet roughening treatment can remove smear in the via hole while forming an uneven anchor on the surface of the insulating layer. preferable. The swelling treatment with the swelling liquid is carried out 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 solution include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Security P (Swelling Dip Security P) and Swelling Dip Security SBU (Swelling Dip Security SBU) manufactured by Atotech Japan Co., Ltd. be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent 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 oxidizing agent include an alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd. and Dozing Solution Security P. The neutralization treatment with a neutralizing solution is carried out by immersing the insulating layer in the neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably 35 to 45 ° C. for 3 to 8 minutes). The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include Reduction Solusin Securigant P manufactured by Atotech Japan Co., Ltd.

The Ra (arithmetic mean roughness) of the surface of the cured product after the roughening treatment of the cured product of the present invention is preferably 400 nm or less, more preferably 300 nm or less, from the viewpoint of enabling the formation of fine wiring. , 200 nm or less is even more preferable, and 100 nm or less is particularly preferable. There is no limit to the lower limit, but it is generally 20 nm or more. The arithmetic mean roughness (Ra value) of the cured product surface 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 B-Coin Sturments.

Then, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as thin film deposition, sputtering, and ion plating can be used. Examples of wet plating include a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having a pattern opposite to that of the conductor layer, and a method of forming a conductor layer only by electroless plating. Be done. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, etc. known to those skilled in the art can be used. Then, by repeating the above-mentioned series of steps a plurality of times, it is possible to manufacture a multilayer printed wiring board in which build-up layers are laminated in multiple stages.

The peeling strength of the plated conductor layer of the cured product obtained by curing the resin composition of the present invention is preferably 0.4 kgf / cm or more, and more preferably 0.5 kgf / cm or more. There is no limit to the upper limit, but it is generally 1.0 kgf / cm or less. For the peeling strength of the plated conductor layer, a conductor layer is formed by plating on the surface of the cured product after the roughening treatment, and the plating peel strength between the surface of the cured product and the conductor layer is measured. Examples of the tensile tester include "AC-50C-SL" manufactured by TSE Co., Ltd.

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

The mounting method of the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Measurement method / evaluation method>
First, various measurement methods and evaluation methods 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 heat-cure the resin composition layer. The cured product was cut into test pieces 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 thermomechanical analyzer (Thermo Plus TMA8310) manufactured by Rigaku Co., Ltd. After the test piece was attached to the apparatus, the test piece was measured twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the glass transition temperature and the average coefficient of linear thermal expansion from 25 ° C to 150 ° C were calculated.

<Preparation of samples for arithmetic mean roughness (Ra value) and peel strength measurement>
(1) Base treatment of inner layer circuit board Both sides of the glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Works, Ltd.) on which the inner layer circuit was formed The copper surface was roughened by etching 1 μm with CZ8100 manufactured by MEC Co., Ltd.

(2) Laminating of Adhesive Films The adhesive films prepared in 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.). Lamination was carried out by reducing the pressure for 30 seconds to an atmospheric pressure of 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition The laminated adhesive film was cured under the curing conditions of 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to form an insulating layer. Then, the PET film was peeled off.

(4) Roughening treatment The inner layer circuit board on which the insulating layer was formed was immersed in a swelling liquid, a swelling dip securigant P containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd., at 60 ° C. for 10 minutes, and then immersed. As a roughening solution, soak in Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Atotech Japan Co., Ltd. at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan. It was immersed in Reduction Solusin Securigant P manufactured by Co., Ltd. at 40 ° C. for 5 minutes. After drying at 80 ° C. for 30 minutes, the arithmetic mean roughness (Ra value) and the root mean square roughness (Rq value) were measured on the surface of the insulating layer after the roughening treatment.

(5) Plating by Semi-Additive Method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board is immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution. It was immersed at 25 ° C. for 20 minutes. After heating at 150 ° C. for 30 minutes to perform annealing treatment, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 25 μm. Next, the annealing treatment was performed at 180 ° C. for 30 minutes. The peel strength (peel strength) of the plated conductor layer was measured for this circuit board.

<Measurement of arithmetic mean roughness (Ra value) after roughening treatment>
Using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Sturments Co., Ltd.), the Ra value was determined by the numerical value obtained with the measurement range of 121 μm × 92 μm by the VSI contact mode and the 50x lens. Then, the average value of 10 points was obtained and used as the measured value.

<Measurement of peeling strength (peeling strength) of plated conductor layer>
Make a notch with a width of 10 mm and a length of 100 mm in the conductor layer of the circuit board, peel off one end of the notch, grasp it with a gripper (TSE Co., Ltd., Autocom type tester AC-50CSL), and keep it at room temperature. Then, the load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min was measured.

<Measurement of melt viscosity>
The melt viscosity of the resin composition layer at 100 ° C. in the adhesive films produced in Examples and Comparative Examples was measured. Using UBM Co., Ltd. model Rheosol-G3000, using a parallel plate with a resin amount of 1 g and a diameter of 18 mm, the starting temperature is from 60 ° C to 200 ° C, and the temperature rise rate is 5 ° C / min. The melt viscosity was measured under the measurement conditions of a temperature interval of 2.5 ° C. and a vibration of 1 Hz / deg.

<Lamability test>
The adhesive films produced in Examples and Comparative Examples were subjected to L (line: wiring width) / S (space: spacing) with a conductor thickness of 35 μm using a batch type vacuum pressurizing laminator MVLP-500 (manufactured by Meiki Co., Ltd.). Width) = 160/160 μm laminated on a comb-shaped conductor pattern. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under curing conditions of 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to form an insulating layer. The value of the unevenness difference (Rt: maximum peak-to-valley) between the conductor and the other part of the insulating layer is determined by using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Sturments) in VSI contact mode. It was determined by the numerical value obtained by setting the measurement range to 1.2 mm × 0.91 mm with a 10x lens. The case where the unevenness difference between the conductor and the other part after laminating was 3.0 μm or less was evaluated as ◯, and the case where the unevenness difference between the conductor and the other part after laminating was larger than 3.0 μm was evaluated as ×.

[Example 1]
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.) and 8 parts of biphenyl aralkyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), 8 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN-475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), phenoxy resin ("YX6954BH30" (weight average molecular weight 38000) manufactured by Japan Epoxy Resin Co., Ltd.) by mass of MEK and cyclohexanone Eight parts of a resin solution having a non-volatile content of 30% by mass dissolved in a mixed solvent having a ratio of 1: 1) were heated and dissolved in 8 parts of MEK and 8 parts of cyclohexanone with stirring. There, 26 parts of an active ester-based curing agent (active group equivalent 223, a toluene solution of 65% by mass of a non-volatile component, "HPC8000-65T" manufactured by DIC Co., Ltd.), 1-benzyl-2-phenylimidazole as a curing accelerator ( 1 part of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., spherical silica ("SOC1" manufactured by Admatex Co., Ltd. (with hexamethyldisilazane treatment, average particle size 0.25 μm, specific gravity 2.2 g / m ³ )) 84 parts of N-Phenyl-3-aminopropyltrimethoxysilane (manufactured by Shinetsu Chemical Co., Ltd., "KBM573"), with an average linear thermal expansion rate of 300 ppb / from 30 ° C to 150 ° C. Spherical glass filler below ° C (“AZ filler” manufactured by Asahi Glass Co., Ltd. (linear thermal expansion rate (average value at 30-150 ° C): titanium-doped spherical glass filler at 0.2 ppm / ° C, average particle size 0.2 μm , Specific gravity 2.2 g / m ³ ) was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) 36 parts were mixed and uniformly mixed with a high-speed rotating mixer. Dispersed to prepare a resin varnish. Next, it was applied on polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) with a die coater so that the thickness of the resin composition after drying was 40 μm, and the temperature was 80 to 120 ° C. (average 100). It was dried at (° C.) for 6 minutes (residual solvent amount of about 2% by mass). Next, a polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition layer and wound into a roll. The roll-shaped adhesive film was slit to a width of 507 mm, and a sheet-shaped adhesive film having a size of 507 mm × 336 mm was obtained from this slit.

[Example 2]
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.) and 8 parts of biphenyl aralkyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), 8 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN-475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), phenoxy resin ("YX6954BH30" (weight average molecular weight 38000) manufactured by Japan Epoxy Resin Co., Ltd.) by mass of MEK and cyclohexanone 8 parts (resin solution having a non-volatile content of 30% by mass) dissolved in a mixed solvent having a ratio of 1: 1 was heated and dissolved in 10 parts of MEK and 10 parts of cyclohexanone with stirring. There, 26 parts of an active ester-based curing agent (active group equivalent 223, a toluene solution of 65% by mass of a non-volatile component, "HPC8000-65T" manufactured by DIC Co., Ltd.), 1-benzyl-2-phenylimidazole as a curing accelerator ( 1 part of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., spherical silica ("SOC1" manufactured by Admatex Co., Ltd. (with hexamethyldisilazane treatment, average particle size 0.25 μm, specific gravity 2.2 g / m ³ )) 84 parts of N-Phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), with an average linear thermal expansion rate of 300 ppb / from 30 ° C to 150 ° C. Zirconium phosphate-based filler at ° C or lower (“ZWP” manufactured by Kyoritsu Material Co., Ltd. (linear thermal expansion rate (average value at 30-150 ° C): -0.3 ppm / ° C, average particle size 2.3 μm, crushed form, 62 parts of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") surface-treated with a specific gravity of 3.8 g / m ³ )) was mixed and uniformly mixed with a high-speed rotating mixer. Dispersed to prepare a resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

[Example 3]
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.) and 8 parts of biphenyl aralkyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), 8 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN-475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), phenoxy resin ("YX6954BH30" (weight average molecular weight 38000) manufactured by Japan Epoxy Resin Co., Ltd.) by mass of MEK and cyclohexanone 8 parts (resin solution having a non-volatile content of 30% by mass) dissolved in a mixed solvent having a ratio of 1: 1 was heated and dissolved in 10 parts of MEK and 10 parts of cyclohexanone with stirring. There, 26 parts of an active ester-based curing agent (active group equivalent 223, a toluene solution of 65% by mass of a non-volatile component, "HPC8000-65T" manufactured by DIC Co., Ltd.), 1-benzyl-2-phenylimidazole as a curing accelerator ( 1 part of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., spherical silica ("SOC1" manufactured by Admatex Co., Ltd. (with hexamethyldisilazane treatment, average particle size 0.25 μm, specific gravity 2.2 g / m ³ )) 84 parts of N-Phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), with an average linear thermal expansion rate of 300 ppb / from 30 ° C to 150 ° C. Crushed glass filler below ° C (“DL7400” manufactured by Nippon Electric Glass Co., Ltd. (linear thermal expansion rate (average value at 30-150 ° C): -1.1 ppm / ° C, average particle size 4.8 μm, specific gravity 2. 41 parts of 5 g / m ³ ) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") was mixed and uniformly dispersed with a high-speed rotating mixer. , A resin varnish was prepared. Next, an adhesive film was obtained in the same manner as in Example 1.

[Example 4]
10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.) and 18 parts of biphenyl aralkyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), Naphthalene type epoxy resin (epoxy equivalent 144, "EXA4032SS" manufactured by DIC Co., Ltd.) 3 parts, naphthalene type tetrafunctional epoxy resin (epoxy equivalent 162, manufactured by DIC Co., Ltd. "HP-4700") 5 parts, phenoxy resin (Japan A resin solution containing 30% by mass of a non-volatile content prepared by dissolving "YX6954BH30" (weight average molecular weight 38000) manufactured by Epoxy Resin Co., Ltd. in a mixed solvent having a mass ratio of methyl ethyl ketone (hereinafter abbreviated as "MEK") and cyclohexanone of 1: 1. ) 18 parts were heated and dissolved in 12 parts of MEK and 12 parts of cyclohexanone with stirring. There, 9 parts of naphthol aralkyl curing agent (phenolic hydroxyl group equivalent 215, "SN485" manufactured by Nippon Steel & Sumitomo Metal Corporation), phenol novolac curing agent (phenolic hydroxyl group equivalent 120, "LA7052" manufactured by DIC Co., Ltd.). 15 parts of MEK solution with a solid content of 60%), 0.2 parts of 4-dimethylaminopyridine as a curing accelerator, spherical silica (“SOC1” manufactured by Admatex Co., Ltd. (with hexamethyldisilazane treatment, average particle size) 0.25 μm, specific gravity 2.2 g / m ³ )) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”), 119 parts, 30 ° C to 150 ° C Spherical glass filler with an average linear thermal expansion rate of 300 ppb / ° C or less (“AZ filler” manufactured by Asahi Glass Co., Ltd. (linear thermal expansion rate (average value of 30-150 ° C): 0.2 ppm / ° C) Titanium-doped spherical glass filler, average particle size 0.2 μm, specific gravity 2.2 g / m ³ )) was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.). 51 parts of the substance was mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

[Example 5]
6 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.) and 16 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN-475V" manufactured by Nippon Steel & Sumitomo Metal Corporation) , Naphthalene type epoxy resin (epoxy equivalent 144, "EXA4032SS" manufactured by DIC Co., Ltd.) 9 parts, naphthylene ether type epoxy resin (epoxy equivalent 266, "EXA7311" manufactured by DIC Co., Ltd.) 6 parts, phenoxy resin (Japan Epoxy) 5 parts of "YX6954BH30" (weight average molecular weight 38000) manufactured by Resin Co., Ltd. dissolved in a mixed solvent having a mass ratio of MEK and cyclohexanone of 1: 1), 15 parts of MEK and 15 parts of cyclohexanone. The epoxy was dissolved by heating while stirring. There, 20 parts of a prepolymer of bisphenol A dicyanate (cyanate equivalent 235, MEK solution of 75% by mass of non-volatile component, Ronza Japan Co., Ltd. "BA230S75"), phenol novolac type polyfunctional cyanate ester resin (cyanate equivalent 124, non-volatile component). 80% by mass MEK solution, 8 parts of "PT30" manufactured by Ronza Japan Co., Ltd., active ester-based curing agent (active group equivalent 223, toluene solution of 65% by mass of non-volatile component, "HPC8000-65T" manufactured by DIC Co., Ltd. ) 12 parts, 0.02 parts of 4-dimethylaminopyridine as a curing accelerator, 4 parts of 1% by mass MEK solution of cobalt (III) acetylacetonate (manufactured by Tokyo Kasei Co., Ltd.), spherical silica (Admatex Co., Ltd.) ) "SOC1" (with hexamethyldisilazane treatment, average particle size 0.25 μm, specific gravity 2.2 g / m ³ )) was N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., ". 140 parts of "KBM573"), spherical glass filler with an average linear thermal expansion rate of 300 ppb / ° C or less between 30 ° C and 150 ° C ("AZ filler" manufactured by Asahi Glass Co., Ltd. (linear thermal expansion rate) (Average value at 30-150 ° C.): Titanium-doped spherical glass filler at 0.2 ppm / ° C., average particle size 0.2 μm, specific gravity 2.2 g / m ³ ))) with N-phenyl-3-aminopropyltrimethoxy 60 parts of silane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

[Example 6]
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.) and 8 parts of biphenyl aralkyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), 8 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN-475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), phenoxy resin ("YX6954BH30" (weight average molecular weight 38000) manufactured by Japan Epoxy Resin Co., Ltd.) by mass of MEK and cyclohexanone Eight parts of a resin solution having a non-volatile content of 30% by mass dissolved in a mixed solvent having a ratio of 1: 1) were heated and dissolved in 8 parts of MEK and 8 parts of cyclohexanone with stirring. There, 26 parts of an active ester-based curing agent (active group equivalent 223, toluene solution of 65% by mass of non-volatile component, "HPC8000-65T" manufactured by DIC Co., Ltd.), 1-benzyl-2-phenylimidazole as a curing accelerator ( 1 part of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., spherical glass filler with an average coefficient of linear thermal expansion of 300 ppb / ° C or less between 30 ° C and 150 ° C ("AZ filler" manufactured by Asahi Glass Co., Ltd. (wire) Coefficient of thermal expansion (average value at 30-150 ° C): 0.2 ppm / ° C titanium-doped spherical glass filler, average particle size 0.2 μm, specific gravity 2.2 g / m ³ ))) with N-phenyl-3-amino 105 parts of propyltrimethoxysilane (“KBM573” manufactured by Shinetsu Chemical Co., Ltd.) surface-treated was mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

[Comparative Example 1]
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, "jER828US" manufactured by Japan Epoxy Resin Co., Ltd.) and 8 parts of biphenyl aralkyl type epoxy resin (epoxy equivalent 291, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), 8 parts of naphthol type epoxy resin (epoxy equivalent 332, "ESN-475V" manufactured by Nippon Steel & Sumitomo Metal Corporation), phenoxy resin ("YX6954BH30" (weight average molecular weight 38000) manufactured by Japan Epoxy Resin Co., Ltd.) by mass of MEK and cyclohexanone 8 parts (resin solution having a non-volatile content of 30% by mass) dissolved in a mixed solvent having a ratio of 1: 1 was heated and dissolved in 12 parts of MEK and 12 parts of cyclohexanone while stirring. There, 26 parts of an active ester-based curing agent (active group equivalent 223, a toluene solution of 65% by mass of a non-volatile component, "HPC8000-65T" manufactured by DIC Co., Ltd.), 1-benzyl-2-phenylimidazole as a curing accelerator ( 1 part of "1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., spherical silica ("SOC1" manufactured by Admatex Co., Ltd. (with hexamethyldisilazane treatment, average particle size 0.25 μm, specific gravity 2.2 g / m ³ )) Was mixed with 150 parts of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., surface-treated with "KBM573", and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

As is clear from this result, the resin composition of the present invention is a resin that provides a cured product having a low coefficient of linear thermal expansion, low roughness and high peel strength, and a sheet-like laminated material having excellent laminating properties. The composition can be provided.

Claims (20)

A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a filler.
(C) The filler is at least
(C-1) Contains a first filler having an average coefficient of linear thermal expansion of 300 ppb / ° C or less between 30 ° C. and 150 ° C.
(C-1) The first filler is a titanium-doped glass filler.
(C-1) The average particle size of the first filler is 5 μm or less.
The content of the first filler (C-1) is 5 to 80% by volume when the non-volatile component in the resin composition is 100% by volume.
The content of the filler in the resin composition is 40% by volume or more when the non-volatile component in the resin composition is 100% by volume.
Resin composition. The resin composition according to claim 1, wherein the non-volatile component in the resin composition is 100% by volume, and the first filler (C-1) is contained in an amount of 5 to 70% by volume. (C-1) The resin composition according to claim 1 or 2, wherein the average particle size of the first filler is 0.01 μm or more. (C-1) The resin composition according to claim 1 or 2, wherein the average particle size of the first filler is 0.1 μm or more. (C-1) The resin composition according to any one of claims 1 to 4, wherein the first filler has a specific gravity of 1 to 7 g / cm ³ . (C-1) The resin composition according to any one of claims 1 to 5, wherein the first filler is a spherical inorganic filler or a crushed inorganic filler. The (C) filler contains the (C-2) second filler.
(C-2) The second filler is
Silica, 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, One or more selected from the group consisting of magnesium titanate, bismuth titanate, titanium oxide, barium titanate, and calcium titanate.
The resin composition according to any one of claims 1 to 6 . (B) The resin according to any one of claims 1 to 7 , wherein the curing agent is at least one selected from an active ester-based curing agent, a cyanate ester-based curing agent, a phenol-based curing agent, and a naphthol-based curing agent. Composition. (A) Claim 1 that the epoxy resin is a bisphenol A type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a naphthylene ether type epoxy resin, or a mixture of two or more thereof. The resin composition according to any one of 8 to 8 . Any one of claims 1 to 9 , wherein the cured product of the resin composition obtained by curing without containing a sheet-shaped reinforcing base material has an average linear thermal expansion coefficient of 20 ppm or less from 25 ° C. to 150 ° C. The resin composition according to the item. The Ra of the surface of the cured product after the roughening treatment in the cured product of the resin composition is 400 nm or less, and the cured product of the resin composition is formed on the surface of the cured product after the roughening treatment of the cured product. The resin composition according to any one of claims 1 to 10 , wherein a conductor layer is formed by plating, and the plating peel strength between the cured product surface and the conductor layer is 0.4 kgf / cm or more. The resin composition according to any one of claims 1 to 11 , which is used for an insulating layer of a multilayer printed wiring board. An adhesive film containing the resin composition according to any one of claims 1 to 12 . The adhesive film according to claim 13 , wherein the resin composition layer of the adhesive film has a melt viscosity of 35,000 poise or less at 100 ° C. A cured product containing the resin composition according to any one of claims 1 to 12 . The cured product according to claim 15 , wherein the average linear thermal expansion coefficient from 25 ° C. to 150 ° C. is 20 ppm or less. The cured product according to claim 15 or 16 , wherein the Ra on the surface of the cured product after the roughening treatment is 400 nm or less. Claims 15 to 17 , wherein when a conductor layer is formed on the surface of the cured product after the roughening treatment of the cured product, the plating peel strength between the surface of the cured product and the conductor layer is 0.4 kgf / cm or more. The cured product according to any one of the items. A multilayer printed wiring board having the cured product according to any one of claims 15 to 18 . A semiconductor device according to claim 19, wherein a multilayer printed wiring board is used.