JP6582366B2 - Resin composition, adhesive film, cured product, multilayer printed wiring board, semiconductor device, and resin composition for insulating layer - Google Patents

Description

  The present invention relates to a resin composition.

  Multilayer printed wiring boards are widely used in various electronic devices and electronic parts. As a manufacturing technique of a multilayer printed wiring board, a manufacturing method based on a build-up method in which insulating layers and conductor layers are alternately stacked on an inner circuit board provided with circuit conductors is known.

  The manufacturing method by the build-up method is generally performed according to the following procedure. First, a resin composition layer is provided on an inner layer 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 minute irregularities on the surface of the insulating layer. Thereafter, 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 multilayer printed wiring boards, interlayer insulation materials are required to have a low coefficient of thermal expansion in order to prevent delamination and wiring rupture due to differences in thermal expansion between the insulating layer and the conductor layer. In addition, it is known that the linear thermal expansion coefficient is reduced by highly filling a resin composition used for forming an insulating layer (for example, Patent Document 1 and Patent Document 2).

JP 2005-38821 A JP 2006-4854 A

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

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

That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a filler having an average coefficient of linear thermal expansion between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less.
[2] When the non-volatile component in the resin composition is 100% by volume, (C) 5-80% by volume of filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less is included. [1] The resin composition according to [1].
[3] (C) The average particle diameter of the filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less is 0.01 to 10 μm, [1] or [2] Resin composition.
[4] (C) Any one of [1] to [3], wherein the specific linear thermal expansion coefficient between 30 ° C. and 150 ° C. has a specific gravity of 1 to 7 g / cm ³ of 300 ppb / ° C. or less. The resin composition as described.
[5] (C) Any of [1] to [4], wherein the filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. is 300 ppb / ° C. or less is a spherical inorganic filler or a crushed inorganic filler. The resin composition as described.
[6] (C) The filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less is at least one selected from glass fillers and zirconium phosphate fillers. ] The resin composition in any one of [5].
[7] (C) The filler according to any one of [1] to [6], wherein the filler having an average linear thermal expansion coefficient between 300 ° C. and 150 ° C. is 300 ppb / ° C. or less is a titanium-doped glass filler. Resin composition.
[8] Any of [1] to [7], wherein (B) the curing agent is at least one selected from an active ester curing agent, a cyanate ester curing agent, a phenol curing agent, and a naphthol curing agent. The resin composition as 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 curing agent,
(C) The resin composition according to any one of [1] to [8], wherein the filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. is 300 ppb / ° C. or less is a titanium-doped glass filler. .
[10] The average linear thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is 20 ppm or less,
In the cured product of the resin composition, Ra on the surface of the cured product after the roughening treatment is 400 nm or less, and a 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 a plating peel strength between the surface of the cured product 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 for an insulating layer of a multilayer printed wiring 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 resin composition layer of the adhesive film has a melt viscosity at 100 ° C. of 35000 poise or less.
[14] A cured product of the resin composition according to any one of [1] to [11].
[15] The cured product according to [14], wherein an 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 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 cured product surface after the roughening treatment of the cured product, the plating peel strength between the cured product surface and the conductor layer is 0.4 kgf / cm or more. [14] Hardened | cured material in 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 using the multilayer printed wiring board according to [18].
[20] (A) epoxy resin, (B) curing agent, (C) for an insulating layer of a multilayer printed wiring board containing a filler having an average coefficient of linear thermal expansion between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less A resin composition comprising:
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 curing agent,
(C) The filler whose average linear thermal expansion coefficient between 30 degreeC and 150 degreeC is 300 ppb / degrees C or less is a titanium dope type glass filler,
The average linear thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is 20 ppm or less,
In the cured product of the resin composition, Ra on the surface of the cured product after the roughening treatment is 400 nm or less, and a 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 a plating peel strength between the surface of the cured product and the conductor layer is 0.4 kgf / cm or more.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which provides the cured | curing material with high peel strength while having a low thermal expansion coefficient and low roughness, and also the sheet-like laminated material which has the outstanding laminating property can be provided.

  The resin composition of the present invention includes (A) an epoxy resin, (B) a curing agent, and (C) a filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less.

<(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. Naphthol novolac epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthalene tetrafunctional type epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, Glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy Fatty, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, and trimethylol Type epoxy resin and the like. Of these, bisphenol A type epoxy resins, biphenyl aralkyl type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, naphthylene ether type epoxy resins, and mixtures of two or more thereof are preferred. An epoxy resin may be used individually by 1 type, or may use 2 or more types together.

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

  Further, it preferably contains an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) and an epoxy resin that is a solid 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 an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the insulating layer formed by curing the resin composition is also improved.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin are preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin are preferable. More preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “EXA4032SS”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, 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. Resin mixture). 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. A liquid epoxy resin may be used individually by 1 type, or may use 2 or more types together.

  Examples of solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins. 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 more 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) manufactured by DIC Corporation, “ 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), "NC7000L" (naphthol novolak epoxy resin), "NC3000H", "NC3000" manufactured by Nippon Kayaku Co., Ltd. ”,“ NC3000L ”,“ NC310 ” (Biphenyl type epoxy resin), “ESN475V” (naphthol novolak type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., “ESN485” (naphthol novolak type epoxy resin), “YX4000H” manufactured by Mitsubishi Chemical Corporation, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), and the like. In particular, “YX4000HK” (bixylenol type epoxy resin), “NC3000L” (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and “HP7200H” (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation are preferable. . A solid epoxy resin may be used individually by 1 type, or may use 2 or more types together.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in a mass ratio of 1: 0.1 to 1: 4. preferable. By setting the amount ratio of the liquid epoxy resin and the solid epoxy resin in such a range, i) suitable adhesiveness is obtained when used in the form of an adhesive film, and ii) when used in the form of an adhesive film. Sufficient flexibility is obtained, handling properties are improved, and iii) an insulating layer having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to 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 more 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 more preferably 30% by mass when the nonvolatile component in the resin composition is 100% by mass. % To 40% by mass is more preferable.

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

<(B) Curing agent>
The curing agent is not particularly limited as long as it has a function of curing an epoxy resin. For example, an active ester curing agent, a cyanate ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, etc. Can be mentioned. Especially, it is preferable to use 1 or more types selected from an active ester hardener, a cyanate ester hardener, a phenol hardener, and a naphthol hardener, and an active ester hardener is more preferable. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, 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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, 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 a phenol novolac acetylated product, and an active ester compound containing a phenol novolak benzoylated product are preferred. Of these, an active ester compound containing a dicyclopentadiene-type diphenol condensation structure is more preferable.

  More specifically, the active ester curing agent containing a dicyclopentadiene-type diphenol condensation structure includes a compound represented by the following formula (1).

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

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

  As a commercial product of an active ester curing agent, as an active ester compound having a dicyclopentadiene type diphenol condensation structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (DIC Corporation) Manufactured product), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, Examples of the active ester compound containing a benzoylated compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylene bis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), 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; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac, these cyanate resins and partially triazine of prepolymer. Preferable specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins) and “BA230” (part of bisphenol A dicyanate or And a prepolymer which is all triazine-modified into a trimer).

  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. Moreover, from a viewpoint of adhesiveness with a conductor layer (circuit wiring), a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Especially, it is preferable to use a triazine skeleton containing phenol novolak resin as a hardening | curing agent from a viewpoint of heat resistance and adhesiveness (peeling strength) with a conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” 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. "LA7052", "LA7054", "LA3018", etc. manufactured by DIC Corporation.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  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 nonvolatile 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 to 40% by mass.

<(C) Filler whose average linear thermal expansion coefficient between 30 ° C. and 150 ° C. is 300 ppb / ° C. or less>
As a method for measuring the average coefficient of linear thermal expansion between 30 ° C. and 150 ° C. of the filler, for example, it is measured by a known method such as a thermal dilatometer or X-ray diffraction method for detecting the elongation of the sample by a laser interferometer be able to.
“Filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less” is an inorganic filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less. Spherical inorganic fillers and crushed inorganic fillers having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less are more preferable, and average linear thermal expansion between 30 ° C. and 150 ° C. A spherical inorganic filler having a rate of 300 ppb / ° C. or less is more preferable. As specific examples, glass fillers, zirconium phosphate fillers, cordierite fillers, silicon oxide fillers, tungstic acids whose average linear thermal expansion coefficient between 30 ° C. and 150 ° C. is 300 ppb / ° C. or less. Zirconium type filler, manganese nitride type filler, etc. are mentioned. Especially, it is preferable to use 1 or more types selected from a glass filler and a zirconium-phosphate type filler from the point which can make hardened | cured material low roughness and can reduce the melt viscosity of an adhesive film. 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 which are glass forming raw materials of TiO ₂ —SiO ₂ glass are gasified and mixed, and then heated and hydrolyzed (flame hydrolysis) in an oxyhydrogen flame. TiO ₂ —SiO ₂ glass fine particles obtained by decomposition). Such a titanium-doped glass filler can be produced by the method described in International Publication No. 2010/134449. Examples of commercially available products include “AZ filler” (linear thermal expansion) manufactured by Asahi Glass Co., Ltd. Rate (average value of 30 to 150 ° C.): 0.2 ppm / ° C. titanium-doped spherical glass filler). As an example of the commercial item of the said zirconium phosphate type filler, Kyoritsu Material Co., Ltd. "ZWP" (Linear thermal expansion coefficient (average value of 30-150 degreeC): -0.3 ppm / degreeC) is mentioned. As an example of a commercial product of the crushed glass filler, “DL7400” (linear thermal expansion coefficient (average value of 30 to 150 ° C.): −1.1 ppm / ° C.) manufactured by Nippon Electric Glass Co., Ltd. can be mentioned.

  (C) The average particle diameter of the filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less is that the cured product has a low roughness and fine wiring can be formed. From the viewpoint of improving the laminating property by improving the fluidity of the film, 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 The range of 3 μm is even more preferable. The average particle diameter of the filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the filler can be prepared on a volume basis with a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. A measurement sample in which the filler is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. or the like can be used.

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

  In the resin composition of the present invention, within the range in which the effect of the present invention is exhibited, (C) an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. is 300 ppb / ° C. or less as necessary. Other fillers may be included.

  Examples of fillers other than fillers having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less include, for example, an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. exceeding 300 ppb / ° 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, titanate Examples include calcium, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica is particularly suitable. Moreover, spherical silica is preferable as the silica. A filler may be used individually by 1 type and may be used in combination of 2 or more type. As commercially available spherical fused silica, “SOC2” manufactured by Admatechs Co., Ltd. (average linear thermal expansion coefficient between 30 ° C. and 150 ° C .: 0.5 ppm / ° C.), “SOC1” (30 ° C. to 150 ° C.) The average coefficient of linear thermal expansion up to 0 ° C .: 0.5 ppm / ° C.).

  (C) The volume ratio of the filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less and the 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.

  In the resin composition of the present invention, the content of all fillers (the 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 as follows: When the non-volatile component in the resin composition is 100% by volume, it is preferably 40% by volume or more, and 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, it is preferably 80% by volume or less, more preferably 70% by volume or less, and still more preferably 65% by volume or less.

  In order to improve moisture resistance and dispersibility, the above fillers are silane coupling agents (epoxysilane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, etc.), titanate coupling agents, silazane compounds, etc. Those having been surface-treated with the above surface treatment agent are preferred. You may use these 1 type or in combination of 2 or more types.

  Examples of the epoxysilane coupling agent include glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, and (3,4-epoxycyclohexyl). Examples of aminosilane coupling agents include aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N- (2-aminoethyl). Examples thereof include aminopropyltrimethoxysilane, and examples of the mercaptosilane coupling agent include mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane. You may use these 1 type or in combination of 2 or more types. 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, for example, additives such as thermoplastic resins, curing accelerators and flame retardants.

-Thermoplastic resin-
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

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

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. 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). In addition, “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 "," YL7482 ", etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include 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), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “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, and 0.5% by mass to 10% by mass when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is mass%. By setting the content of the thermoplastic resin within such a range, the viscosity of the resin composition becomes appropriate, and a uniform resin composition having a thickness and a bulk property 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. A hardening accelerator and a metal type hardening accelerator are preferable.

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

  Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 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 curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 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 trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (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 Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  Although it does not specifically limit as a metal type hardening accelerator, For example, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. 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. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more. As the metal-based curing accelerator, an organic cobalt complex is preferably used, and in particular, cobalt (III) acetylacetonate is preferably used.

  A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. As for content of a hardening accelerator, when the non-volatile component in a resin composition is 100 mass%, it is preferable to use in 0.01 mass%-3 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. A flame retardant may be used individually by 1 type, or may use 2 or more types together. Although content of a flame retardant is not specifically limited, When the non-volatile component in a resin composition is 100 mass%, 0.5 mass%-10 mass% are preferable, 1 mass%-9 mass% are more preferable, 1.5 mass%-8 mass% are further more preferable.

  The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or stirred by a kneading means such as a triple roll, ball mill, bead mill or 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 sheet-like laminated materials such as adhesive films and prepregs, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding It can be used in a wide range of applications where a resin composition is required, such as materials, semiconductor sealing materials, 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). The resin composition for an insulating layer of a multilayer printed wiring board) or a resin composition for forming a buildup layer of a multilayer printed wiring board can be used more suitably. 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 laminated material>
(Adhesive film)
The adhesive film is obtained by forming a resin composition layer on a support. The adhesive film is a method known to those skilled in the art, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like, further heating, Or it can manufacture by drying an organic solvent by hot air spraying etc. and forming a resin composition layer.

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

  The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do. This resin composition layer is sometimes referred to as a B-stage film, and is not completely cured, so that the curing can further proceed.

  The melt viscosity at 100 ° C. of this resin composition layer is preferably 35000 poise or less, more preferably 20000 poise or less, and more preferably 15000 poise or less from the viewpoint of obtaining an adhesive film having good laminating properties and embedding properties. Is more preferably 10000 poise or less, and further preferably 8000 poise or less, 7000 poise or less, 6000 poise or less, or 5000 poise or less from the viewpoint of suppressing unevenness on the surface of the insulating layer and improving fine wiring formability. Particularly preferred. Further, from the viewpoint of preventing bleeding at the time of lamination, 500 poise or more is preferable, 1000 poise or more is more preferable, and 1500 poise or more is more preferable. Since laminating the resin composition layer is usually performed at around 100 ° C., the laminating property of the adhesive film can be evaluated by the melt viscosity value at 100 ° C.

  The melt viscosity at 100 ° C. of the resin composition layer of the present invention can be measured by a dynamic viscoelastic method. Specifically, a parallel plate having a resin amount of 1 g and a diameter of 18 mm is used, and the measurement conditions are a start temperature of 60 ° C. to 200 ° C., a temperature increase rate of 5 ° C./min, a measurement temperature interval of 2.5 ° C., and vibration of 1 Hz / deg By measuring the dynamic viscoelasticity at, the melt viscosity at 100 ° C. of the resin composition layer can be measured. Examples of such a dynamic viscoelasticity measuring apparatus include model Rhesol-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 still more preferable.

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. Among these, from the viewpoint 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 treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  The thickness of the support is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more in terms of improved handling properties. Further, from the viewpoint of improving cost performance and enabling efficient drilling when drilling from the 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 according to the support can be further laminated on the surface of the resin composition layer opposite to the surface to 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. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

(Prepreg)
The prepreg can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-curing it. That is, it can be set as the prepreg which will be in the state which impregnated the sheet-like reinforcement base material with the resin composition of this invention. As a sheet-like reinforcement base material, what consists of a fiber currently used as prepreg fibers, such as glass cloth and an aramid fiber, can be used, for example. And what formed the prepreg on the support body is suitable.

In the hot melt method, the resin composition is once coated on a support without being dissolved in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or directly applied to a sheet-like reinforcing substrate by a die coater. Thus, a prepreg is manufactured. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying. Alternatively, the adhesive film can be prepared by continuously laminating the adhesive film from both sides of the sheet-like reinforcing substrate under heating and pressure conditions. A support, a protective film, and 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 for producing a multilayer printed wiring board using the sheet-like laminated material produced as described above will be described.

  First, a sheet-like laminated material is laminated (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, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

When the sheet-like laminated material has a protective film, after removing the protective film, the sheet-like laminated material and the circuit board are preheated as necessary, while pressing and heating the sheet-like laminated material. Laminate to circuit board. In a preferred embodiment, the sheet-like laminated material is laminated to a circuit board under reduced pressure by a vacuum laminating method. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

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

Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for 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 metal plate such as a heated SUS plate from the support layer side. The pressing condition is that the degree of vacuum is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the bleeding of the resin. For example, the first stage press is performed at a temperature of 70 to 150 ° C. and the pressure is within a range of 1 to 15 kgf / cm ^2. The second stage press is performed at a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm 2. ^It is preferable to carry out in the range of ² . The time for each stage is preferably 30 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.), 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 from 25 ° C. to 150 ° C. of the cured product is preferably 20 ppm or less, preferably 17 ppm or less, and more preferably 14 ppm or less. Although there is no restriction | limiting in a lower limit, generally it will be 4 ppm or more. The linear thermal expansion coefficient can be measured by performing thermomechanical analysis by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310).

  Moreover, when the sheet-like laminated material of the present invention is laminated on a circuit board and a cured product is created by thermosetting, the unevenness difference (undulation) between the cured product surface on the circuit and the surface other than on the circuit is: It is preferable that it is 3 micrometers or less. This unevenness difference can be measured by using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoins Instruments).

  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 can be performed by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. Among these, drilling with a laser such as a carbon dioxide laser or a YAG laser is the most common method. Also, a sheet-like laminated material is laminated on a circuit board, the resin composition layer is thermally cured to form an insulating layer, and a via hole is formed by drilling the insulating layer formed on the circuit board from above the support. Thus, it is preferable to produce a multilayer printed wiring board, and it is preferable to peel the support after drilling. Thus, by forming a via hole by drilling from the support, it is possible to suppress the occurrence of smear. 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 still 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 a method in which a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution are performed in this order. Either dry or wet roughening treatment may be adopted, but wet roughening treatment can remove smear in the via hole while forming uneven anchors on the insulating layer surface. preferable. 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 alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securigans P (Swelling Dip Securigans SBU) and Swelling Dip Securigans 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 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 permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing the insulating layer in the neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  The Ra (arithmetic mean roughness) of the cured product surface 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 fine wiring formation. More preferably, it is 200 nm or less, and particularly preferably 100 nm or less. The lower limit is not limited, but is generally 20 nm or more. The arithmetic average roughness (Ra value) of the cured product surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. And the multilayer printed wiring board which laminated | stacked the buildup layer in multiple stages can be manufactured by repeating the above-mentioned series of processes several times.

  The peel 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. Although there is no restriction | limiting in an upper limit, Generally it will be 1.0 kgf / cm or less. As for the peel strength of the plated conductor layer, a conductor layer is formed on the cured product surface after the roughening treatment by plating, and the plating peel strength between the cured product surface and the conductor layer is measured. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.

<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 in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for 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 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).

  EXAMPLES The present invention will be specifically described below 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 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 load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310). After mounting the test piece on the apparatus, the test piece was measured twice continuously 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 linear thermal expansion coefficient from 25 ° C. to 150 ° C. were calculated.

<Preparation of Sample for Measuring Average Roughness (Ra Value) and Peel Strength>
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by etching 1 μm with CZ8100 manufactured by MEC.

(2) Lamination of adhesive film The adhesive films prepared in Examples and Comparative Examples were laminated on both surfaces of the inner circuit board using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

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

(4) Roughening treatment The inner layer circuit board on which the insulating layer has been formed is immersed in a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P, which is a swelling liquid, at 60 ° C. for 10 minutes, and then As a roughening solution, it is immersed in an Atotech Japan Co., Ltd. Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan It was immersed for 5 minutes at 40 ° C. in Reduction Solucine Securigant P manufactured by Co., Ltd. After drying at 80 ° C. for 30 minutes, arithmetic surface roughness (Ra value) and 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 in an electroless copper plating solution. It was immersed for 20 minutes at 25 ° C. After annealing at 150 ° C. for 30 minutes, an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm. Next, annealing treatment was performed at 180 ° C. for 30 minutes. The circuit board was measured for peel strength (peel strength) of the plated conductor layer.

<Measurement of arithmetic average roughness (Ra value) after roughening>
Using a non-contact type surface roughness meter (Veeco Instruments Inc. WYKO NT3300), VS I mode, was determined Ra values numerically obtained the measurement range by 50-fold the lens as 121μm × 92μm. And it was set as the measured value by calculating | requiring the average value of 10 points | pieces.

<Measurement of peel strength (peel 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, and hold it with a gripping tool (TSE Corp., Autocom type testing machine AC-50CSL). The load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min was measured.

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

<Lamination test>
The adhesive films produced in the examples and comparative examples were prepared using a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.) with a conductor thickness of 35 μm and L (line: wiring width) / S (space: spacing). Lamination was performed on a comb-like conductor pattern having a width of 160/160 μm. Lamination was performed 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. Unevenness difference of the conductor and on the other portions of the insulating layer: the value of (Rt largest peak-to-valley) is using a non-contact type surface roughness meter (Veeco Instruments Inc. WYKO NT3300), VS I M o And a numerical value obtained by setting the measurement range to 1.2 mm × 0.91 mm with a 10 × lens. The case where the unevenness difference between the conductor and the other part after lamination was 3.0 μm or less after lamination was evaluated as “◯”, and the case where the unevenness difference between the conductor and the other part after lamination 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 Resins Co., Ltd.) and 8 parts 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 & Sumikin Chemical Co., Ltd.), phenoxy resin (“YX6954BH30” manufactured by Japan Epoxy Resin Co., Ltd.) (weight average molecular weight 38000) mass of MEK and cyclohexanone 8 parts of a resin solution having a non-volatile content of 30% by mass dissolved in a mixed solvent with a ratio of 1: 1) was dissolved in 8 parts of MEK and 8 parts of cyclohexanone with stirring. Thereto, 26 parts of an active ester-based curing agent (active group equivalent 223, 65 mass% nonvolatile component toluene solution, “HPC8000-65T” manufactured by DIC Corporation), 1-benzyl-2-phenylimidazole ( Shikoku Kasei Kogyo Co., Ltd. "1B2PZ") 1 part, spherical silica (Admatex Co., Ltd. "SOC1" (with hexamethyldisilazane treatment, average particle size 0.25μm, specific gravity 2.2g / m ³ )) Of which was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”), and the average linear thermal expansion coefficient between 30 ° C. and 150 ° C. was 300 ppb / Spherical glass filler at a temperature of ℃ or lower ("AZ filler" manufactured by Asahi Glass Co., Ltd.) 36 parts of a glass filler having an average particle size of 0.2 μm and a specific gravity of 2.2 g / m ³ ) treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) The mixture was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, it was coated on a 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 ) For 6 minutes (residual solvent amount of about 2% by mass). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition layer. The roll-like adhesive film was slit to a width of 507 mm, and a sheet-like adhesive film having a size of 507 mm × 336 mm was obtained therefrom.

[Example 2]
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, “jER828US” manufactured by Japan Epoxy Resins Co., Ltd.) and 8 parts 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 & Sumikin Chemical Co., Ltd.), phenoxy resin (“YX6954BH30” manufactured by Japan Epoxy Resin Co., Ltd.) (weight average molecular weight 38000) mass of MEK and cyclohexanone 8 parts of a resin solution having a nonvolatile content of 30% by mass dissolved in a mixed solvent having a ratio of 1: 1) was dissolved in 10 parts of MEK and 10 parts of cyclohexanone with stirring. Thereto, 26 parts of an active ester-based curing agent (active group equivalent 223, 65 mass% nonvolatile component toluene solution, “HPC8000-65T” manufactured by DIC Corporation), 1-benzyl-2-phenylimidazole ( Shikoku Kasei Kogyo Co., Ltd. "1B2PZ") 1 part, spherical silica (Admatex Co., Ltd. "SOC1" (with hexamethyldisilazane treatment, average particle size 0.25μm, specific gravity 2.2g / m ³ )) Of which was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”), and the average linear thermal expansion coefficient between 30 ° C. and 150 ° C. was 300 ppb / Zirconium phosphate filler (Kyoritsu Material Co., Ltd. “ZWP” (linear thermal expansion coefficient (average value of 30-150 ° C.)): −0.3 ppm / ° C., average Particle size 2.3 μm, crushed, specific gravity 3.8 g / m ³ )) surface treated with N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 62 parts The mixture was mixed and dispersed uniformly 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 3]
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, “jER828US” manufactured by Japan Epoxy Resins Co., Ltd.) and 8 parts 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 & Sumikin Chemical Co., Ltd.), phenoxy resin (“YX6954BH30” manufactured by Japan Epoxy Resin Co., Ltd.) (weight average molecular weight 38000) mass of MEK and cyclohexanone 8 parts of a resin solution having a nonvolatile content of 30% by mass dissolved in a mixed solvent having a ratio of 1: 1) was dissolved in 10 parts of MEK and 10 parts of cyclohexanone with stirring. Thereto, 26 parts of an active ester-based curing agent (active group equivalent 223, 65 mass% nonvolatile component toluene solution, “HPC8000-65T” manufactured by DIC Corporation), 1-benzyl-2-phenylimidazole ( Shikoku Kasei Kogyo Co., Ltd. "1B2PZ") 1 part, spherical silica (Admatex Co., Ltd. "SOC1" (with hexamethyldisilazane treatment, average particle size 0.25μm, specific gravity 2.2g / m ³ )) Of which was surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”), and the average linear thermal expansion coefficient between 30 ° C. and 150 ° C. was 300 ppb / Crushed glass filler (° C or less “DL7400” (linear thermal expansion coefficient (average value of 30 to 150 ° C.): −1.1 ppm / ° C., average particle size) 4.8 μm, specific gravity 2.5 g / m ³ ) was mixed with 41 parts of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., “KBM573”), and 41 parts were mixed. A resin varnish was prepared by uniformly dispersing with a mixer. 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.) 3 parts of naphthalene type epoxy resin (epoxy equivalent 144, “EXA4032SS” manufactured by DIC Corporation), 5 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 162, “HP-4700” manufactured by DIC Corporation), phenoxy resin (Japan) Epoxy resin "YX6954BH30" (weight average molecular weight 38000) resin solution having a nonvolatile content of 30% by mass dissolved in a mixed solvent of methyl ethyl ketone (hereinafter abbreviated as "MEK") and cyclohexanone in a mass ratio of 1: 1. ) 18 parts, MEK 12 parts, cyclohe It was dissolved by heating with stirring Sanon 12 parts. There, 9 parts of naphthol aralkyl-based curing agent (phenolic hydroxyl group equivalent 215, “SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), phenol novolac-based curing agent (phenolic hydroxyl group equivalent 120, manufactured by DIC Corporation “LA7052” 15 parts of MEK solution with a solid content of 60%), 0.2 part of 4-dimethylaminopyridine as a curing accelerator, spherical silica ("SOC1" manufactured by Admatechs 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 having an average linear thermal expansion coefficient of up to 300 ppb / ° C. (“AZ filler” manufactured by Asahi Glass Co., Ltd. (linear thermal expansion coefficient (3 0-150 ° C. average value): 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-aminopropyltrimethoxysilane A resin varnish was prepared by mixing 51 parts of the surface treated with (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) and uniformly dispersing with a high-speed rotary mixer. 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 & Sumikin Chemical Co., Ltd.) , 9 parts of naphthalene type epoxy resin (epoxy equivalent 144, “EXA4032SS” manufactured by DIC Corporation), 6 parts of naphthylene ether type epoxy resin (epoxy equivalent 266, “EXA7311” manufactured by DIC Corporation), phenoxy resin (Japan Epoxy) Resin Co., Ltd. “YX6954BH30” (weight average molecular weight 38000) (resin solution having a nonvolatile content of 30% by mass in a mixed solvent having a mass ratio of MEK and cyclohexanone of 1: 1) 5 parts, MEK 15 parts, cyclohexanone 15 The mixture was heated and dissolved with stirring. There, 20 parts of a prepolymer of bisphenol A dicyanate (cyanate equivalent 235, MEK solution with 75% by mass of nonvolatile components, Lonza Japan Co., Ltd. “BA230S75”), phenol novolac type polyfunctional cyanate ester resin (cyanate equivalent 124, nonvolatile components) 80 parts by mass of MEK solution, 8 parts of Lonza Japan Co., Ltd. “PT30”, active ester curing agent (active group equivalent 223, non-volatile component 65% by mass of toluene solution, DIC Corporation “HPC8000-65T” ) 12 parts, 0.02 part of 4-dimethylaminopyridine as a curing accelerator, 4 parts of a 1% by weight MEK solution of cobalt (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.), spherical silica (Admatex Co., Ltd.) "SOC1" (with hexamethyldisilazane treatment, average particle size 0. 5 [mu] m, a specific gravity 2.2 g ^{/ m} 3)) of N- phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., subjected to a surface treatment with "KBM573") 140 parts, from 30 ° C. to 0.99 ° C. Spherical glass filler having an average linear thermal expansion coefficient of 300 ppb / ° C. or less (“AZ filler” manufactured by Asahi Glass Co., Ltd. (linear thermal expansion coefficient (average value of 30 to 150 ° C.): 0.2 ppm / ° C. titanium dope) Type spherical glass filler, 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.) 60 The parts were mixed and dispersed uniformly 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 Resins Co., Ltd.) and 8 parts 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 & Sumikin Chemical Co., Ltd.), phenoxy resin (“YX6954BH30” manufactured by Japan Epoxy Resin Co., Ltd.) (weight average molecular weight 38000) mass of MEK and cyclohexanone 8 parts of a resin solution having a non-volatile content of 30% by mass dissolved in a mixed solvent with a ratio of 1: 1) was dissolved in 8 parts of MEK and 8 parts of cyclohexanone with stirring. Thereto, 26 parts of an active ester-based curing agent (active group equivalent 223, 65 mass% nonvolatile component toluene solution, “HPC8000-65T” manufactured by DIC Corporation), 1-benzyl-2-phenylimidazole ( 1 part of Shikoku Kasei Kogyo Co., Ltd. “1B2PZ”), spherical glass filler having an average linear thermal expansion coefficient between 300 ° C. and 150 ° C. of 300 ppb / ° C. or less (“AZ filler” manufactured by Asahi Glass Co., Ltd.) Coefficient of thermal expansion (average value of 30-150 ° C.): 0.2 ppm / ° C. titanium-doped spherical glass filler, average particle size of 0.2 μm, specific gravity of 2.2 g / m ³ )) 105 parts of a surface treated with propyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and dispersed uniformly 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.

[Comparative Example 1]
5 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 190, “jER828US” manufactured by Japan Epoxy Resins Co., Ltd.) and 8 parts 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 & Sumikin Chemical Co., Ltd.), phenoxy resin (“YX6954BH30” manufactured by Japan Epoxy Resin Co., Ltd.) (weight average molecular weight 38000) mass of MEK and cyclohexanone 8 parts of a resin solution having a nonvolatile content of 30% by mass dissolved in a mixed solvent with a ratio of 1: 1) was dissolved in 12 parts of MEK and 12 parts of cyclohexanone with stirring. Thereto, 26 parts of an active ester-based curing agent (active group equivalent 223, 65 mass% nonvolatile component toluene solution, “HPC8000-65T” manufactured by DIC Corporation), 1-benzyl-2-phenylimidazole ( Shikoku Kasei Kogyo Co., Ltd. "1B2PZ") 1 part, spherical silica (Admatex Co., Ltd. "SOC1" (with hexamethyldisilazane treatment, average particle size 0.25μm, specific gravity 2.2g / m ³ )) Was mixed with N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., “KBM573”, 150 parts) 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 apparent from the results, the resin composition of the present invention is a resin that provides a cured product having a low linear thermal expansion coefficient, a low roughness and a high peel strength, and a sheet-like laminated material having excellent laminating properties. A composition can be provided.

Claims (20)

(A) an epoxy resin, (B) a curing agent, a (C) including a resin composition linear thermal expansion coefficient of the average of 300 ppb / ° C. or less of the filler of between 30 ° C. to 0.99 ° C.,
(C) the average particle size of component Ri 0.1~5μm der,
The average linear thermal expansion coefficient of from 25 ° C. of the cured product of the resin composition obtained by curing without the sheet-like reinforcing substrate to 0.99 ° C. is Ru der less 20 ppm, the resin composition (however, boron nitride Except the resin composition containing).   When the non-volatile component in the resin composition is 100% by volume, (C) 5 to 80% by volume of a filler having an average linear thermal expansion coefficient between 30 ° C. and 150 ° C. of 300 ppb / ° C. or less is included. 1. The resin composition according to 1.   (C) The resin composition of Claim 1 or 2 whose average particle diameter of the average linear thermal expansion coefficient between 30 degreeC and 150 degreeC is 300-3 ppb / degrees C or less is 0.2-3 micrometers. (C) Resin of any one of Claims 1-3 whose specific gravity of the average linear thermal expansion coefficient between 30 to 150 degreeC is 300 ppb / degrees C or less, and whose specific gravity is 1-7 g / cm < ³ >. Composition.   (C) Resin of any one of Claims 1-4 whose filler whose average coefficient of linear thermal expansion between 30 degreeC and 150 degreeC is 300 ppb / degrees C or less is a spherical inorganic filler or a crushed inorganic filler. Composition.   (C) The filler whose average linear thermal expansion coefficient between 30 degreeC and 150 degreeC is 300 ppb / degrees C or less is 1 or more types selected from a glass filler and a zirconium phosphate type filler. The resin composition of any one of these.   (C) Resin composition of any one of Claims 1-6 whose filler whose average linear thermal expansion coefficient between 30 degreeC and 150 degreeC is 300 ppb / degrees C or less is a titanium dope type glass filler. .   (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 curing agent, a cyanate ester curing agent, a phenol curing agent, and a naphthol curing agent. Composition. (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 curing agent,
(C) The resin composition of any one of Claims 1-8 whose filler whose average linear thermal expansion coefficient between 30 degreeC and 150 degreeC is 300 ppb / degrees C or less is a titanium dope type glass filler. . In the cured product of the resin composition, Ra on the surface of the cured product after the roughening treatment is 400 nm or less, and a 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 9, wherein a conductor layer is formed by plating, and a 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 10, which is used for an insulating layer of a multilayer printed wiring board.   The adhesive film containing the resin composition of any one of Claims 1-11.   The adhesive film of Claim 12 whose melt viscosity in 100 degreeC of the resin composition layer of this adhesive film is 35000 poise or less. Hardened | cured material containing the resin composition of any one of Claims 1-11. The hardened | cured material of Claim 14 whose average linear thermal expansion coefficient from 25 degreeC to 150 degreeC is 17 ppm or less.   The hardened | cured material of Claim 14 or 15 whose Ra of the hardened | cured material surface after a roughening process is 400 nm or less.   The plating peel strength between the cured product surface and the conductor layer is 0.4 kgf / cm or more when a conductor layer is formed by plating on the cured product surface after the roughening treatment of the cured product. Hardened | cured material of any one of Claims.   The multilayer printed wiring board which has a hardened | cured material of any one of Claims 14-17.   A semiconductor device using the multilayer printed wiring board according to claim 18. (A) Epoxy resin, (B) curing agent, (C) Resin composition for insulating layer of multilayer printed wiring board containing filler having an average linear thermal expansion coefficient of 30 ppb / ° C. or less between 30 ° C. and 150 ° C. Because
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 curing agent,
(C) The filler whose average linear thermal expansion coefficient between 30 degreeC and 150 degreeC is 300 ppb / degrees C or less is a titanium dope type glass filler,
The average linear thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is 20 ppm or less,
In the cured product of the resin composition, Ra on the surface of the cured product after the roughening treatment is 400 nm or less, and a 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 a plating peel strength between the surface of the cured product and the conductor layer is 0.4 kgf / cm or more.