JP2019123799A - Resin composition for interlayer insulation layer, resin film for interlayer insulation layer, multilayer printed wiring board, semiconductor package and method for manufacturing multilayer printed wiring board - Google Patents

Abstract

To provide a resin composition for an interlayer insulation layer achieving both low thermal expansion property and adhesiveness to a conductor layer, a resin film for an interlayer insulation layer using the resin composition for an interlayer insulation layer, a multilayer printed wiring board, a semiconductor package and a method for manufacturing a multilayer printed wiring board.SOLUTION: The resin composition for an interlayer insulation layer comprises (A) a thermosetting resin and (B) an inorganic filler. The content of the (B) inorganic filler in the resin composition for an interlayer insulation layer is 55 to 90 vol.%. The (B) inorganic filler comprises (B1) a nano-filler and (B2) a spherical filler having an average particle diameter larger than that of the (B1) nano-filler. The content of the (B1) nano-filler in the resin composition for an interlayer insulation layer is 0.3 to 2 vol.%. The present invention also provides a resin film for an interlayer insulation layer using the above resin composition for an interlayer insulation layer, a multilayer printed wiring board, a semiconductor package and a method for manufacturing a multilayer printed wiring board.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition for interlayer insulating layer, a resin film for interlayer insulating layer, a multilayer printed wiring board, a semiconductor package, and a method for producing a multilayer printed wiring board.

In recent years, in multilayer printed wiring boards used for electronic devices, communication devices, etc., demands for speeding up of arithmetic processing speed as well as miniaturization, weight reduction and high density of wiring are increasing. Along with this, as a method of manufacturing a multilayer printed wiring board, a build-up type manufacturing technology in which interlayer insulating layers are alternately stacked on a wiring layer of a circuit board has attracted attention.
The buildup layer is required to have a low thermal expansion coefficient (low CTE) from the demand for processing dimensional stability and reduction of warpage after semiconductor mounting, and efforts are being made to achieve low CTE ( For example, refer to patent documents 1-3). As the most mainstream method, there is a method of highly filling the thermosetting resin with an inorganic filler (for example, using 40% by mass or more of the buildup layer as a silica filler).

However, in the buildup layer highly filled with the inorganic filler, the inorganic filler is exposed to the surface after the wet roughening treatment step, and the adhesion with the conductor layer formed on the buildup layer thereafter decreases. A problem arises.
To address the above problems, for example, a method is considered in which the adhesion between the low CTE and the conductor layer is made compatible by separating the buildup layer into two layers, the interlayer insulating layer and the adhesion auxiliary layer, and separating the functions. (E.g., Patent Document 4).

Japanese Patent Application Publication No. 2006-527920 JP, 2007-87982, A JP, 2009-280758, A JP, 2016-060881, A

  However, the method of forming a buildup layer in two layers has a problem of high cost, and from the viewpoint of workability and productivity, a material that can achieve both low CTE and adhesion between a conductor layer even in a single layer is required. There is.

  The present invention has been made to solve such problems, and provides a resin composition for an interlayer insulating layer having both low thermal expansion and adhesion to a conductor layer, and the resin composition for the interlayer insulating layer. An object of the present invention is to provide a manufacturing method of a resin film for an interlayer insulating layer, a multilayer printed wiring board, a semiconductor package and a multilayer printed wiring board used.

The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, the resin composition for interlayer insulating layer containing a specific amount of a specific inorganic filler exhibits low thermal expansion and adhesion with a conductor layer. I found it to be compatible. That is, the present invention relates to the following [1] to [14].
[1] A resin composition for an interlayer insulating layer comprising (A) a thermosetting resin and (B) an inorganic filler,
The content of the (B) inorganic filler in the interlayer insulating layer resin composition is 55 to 90% by volume,
(B) The inorganic filler contains (B1) nanofillers and (B2) spherical fillers having an average particle diameter larger than the (B1) nanofillers,
The resin composition for interlayer insulation layers whose content of the (B1) nano filler in the resin composition for interlayer insulation layers is 0.3-2 volume%.
[2] The resin composition for an interlayer insulating layer according to the above [1], wherein the average particle diameter of the (B1) nanofiller is 150 nm or less.
[3] The resin composition for an interlayer insulating layer according to the above [1] or [2], wherein the content of the (B2) spherical filler in the resin composition for an interlayer insulating layer is 54 to 88% by volume.
[4] The resin composition for an interlayer insulating layer according to any one of the above [1] to [3], wherein the (B1) nanofiller is silica.
[5] (B1) The interlayer insulation according to any one of the above [1] to [4], wherein the nanofiller is not subjected to surface treatment or is subjected to surface treatment with a silane coupling agent. Resin composition for layers.
[6] The resin composition for an interlayer insulating layer according to any one of the above [1] to [5], wherein the average particle diameter of the (B2) spherical filler is 0.25 to 3 μm.
[7] (B2) The resin composition for an interlayer insulating layer according to any one of the above [1] to [6], wherein the spherical filler is spherical silica.
[8] (B2) The resin composition for an interlayer insulating layer according to any one of the above [1] to [7], wherein the spherical filler is surface-treated with an aminosilane coupling agent.
[9] A resin composition layer for an interlayer insulating layer, comprising a support and a resin composition layer for an interlayer insulating layer, wherein the resin composition layer for an interlayer insulating layer is the resin composition for an interlayer insulating layer according to any one of the above [1] to [8] A resin film for interlayer insulating layer, which is a layer formed by layer forming a layer.
[10] The resin film for an interlayer insulating layer according to the above [9], wherein the support is a polyethylene terephthalate film and the thickness is 75 μm or less.
[11] The resin film for interlayer insulating layer according to the above [9] or [10], wherein the thickness of the resin composition layer for interlayer insulating layer is 1 to 50 μm.
[12] An interlayer insulation of the resin composition for an interlayer insulating layer according to any one of the above [1] to [8], and the resin film for an interlayer insulating layer according to any of the above [9] to [11] The multilayer printed wiring board containing 1 or more types of hardened | cured material selected from the group which consists of a resin composition layer for layers.
[13] A semiconductor package obtained by mounting a semiconductor element on the multilayer printed wiring board according to the above [12].
[14] A method for producing a multilayer printed wiring board according to the above [12], comprising the step of wet roughening the cured product, wherein the weight reduction of the cured product in the wet roughening process The manufacturing method of the multilayer printed wiring board whose quantity is 1.3 g / m < ² > or less.

  According to the present invention, a resin composition for an interlayer insulating layer having both low thermal expansion and adhesion to a conductor layer, a resin film for an interlayer insulating layer using the resin composition for an interlayer insulating layer, and a multilayer printed wiring board And a method of manufacturing a semiconductor package and a multilayer printed wiring board.

It is a surface SEM photograph (10,000 times) of the interlayer insulation layer (after wet roughening treatment) obtained in Example 1. It is a surface SEM photograph (35,000 times) of the interlayer insulation layer (after wet roughening treatment) obtained in Example 1. It is a surface SEM photograph (10,000 times) of the interlayer insulation layer (after a wet roughening process) obtained by the comparative example 1. FIG.

[Resin composition for interlayer insulating layer]
The resin composition for interlayer insulating layer (hereinafter, also simply referred to as "resin composition") of the present invention comprises (A) a thermosetting resin and (B) an inorganic filler, and a resin composition for an interlayer insulating layer. And the content of the (B) inorganic filler in the resin composition for the interlayer insulating layer is 55 to 90% by volume, and the (B) inorganic filler is (B1) a nanofiller, and B1) A spherical filler having an average particle diameter larger than that of the nanofiller (B2), and the content of the (B1) nanofiller in the interlayer insulating layer resin composition is 0.3 to 2% by volume It is.
The interlayer insulating layer formed from the resin composition for an interlayer insulating layer according to the present invention has an interlayer insulating layer for a printed wiring board, particularly an interlayer for a buildup layer, in order to achieve both low thermal expansion and adhesiveness with a conductor layer. It is suitable as an insulating layer.
Hereinafter, each component which the resin composition of this invention contains is demonstrated.

<(A) Thermosetting resin>
(A) As a thermosetting resin, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, A silicone resin, a triazine resin, a melamine resin etc. are mentioned. Among these, epoxy resins are preferable from the viewpoints of heat resistance, adhesion to a conductor layer, moldability, and electrical insulation.
(A) A thermosetting resin may be used individually by 1 type, and may use 2 or more types together.

  As an epoxy resin, the epoxy resin which has an 2 or more epoxy group in 1 molecule is mentioned preferably, for example. Specific examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin such as bisphenol S epoxy resin; phenol novolac epoxy resin, cresol novolac epoxy resin, dicyclopentadiene novolac epoxy Novolak type epoxy resin such as resin, anthracene novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol S novolac type epoxy resin, aralkyl novolac type epoxy resin, naphthol novolac type epoxy resin; biphenol type epoxy resin, dicyclopentadiene type epoxy Resin, aralkyl type epoxy resin, tert-butyl-catechol type epoxy resin, fluorene type epoxy resin, xanthe Type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins. Among these, from the viewpoint of heat resistance and smear processability, aralkyl novolac epoxy resins are preferable, and aralkyl novolac epoxy resins having a biphenyl skeleton are more preferable.

(A) When a solid epoxy resin is used as a thermosetting resin, the solid epoxy resin is used in combination with a liquid epoxy resin such as bisphenol A epoxy resin or bisphenol F epoxy resin from the viewpoint of the handleability of the obtained resin film. It is preferable to do. In that case, the content ratio (solid epoxy resin / liquid epoxy resin) (mass ratio) is preferably 0.5 to 5 and 1 to 3 from the viewpoint of the handleability, electrical characteristics and heat resistance of the obtained resin film. More preferably, 1.2 to 2 is more preferable. In addition, as said solid epoxy resin, an aralkyl novolak-type epoxy resin is preferable, and as a liquid epoxy resin, bisphenol-A epoxy resin is preferable.
Properties such as “solid” and “liquid” in the present specification mean the state at room temperature (25 ° C.).

  The epoxy resin may be a commercially available product. Commercially available epoxy resins include “NC-3000-H”, “NC-3000-L”, “NC-3100”, and “NC-3000” (trade names, manufactured by Nippon Kayaku Co., Ltd., biphenyl skeleton Novolak type epoxy resin having an epoxy resin), “NC-7000-L” (trade name, manufactured by Nippon Kayaku Co., Ltd., naphthol novolac epoxy resin), “Epiclon (registered trademark) N 673” (trade name, manufactured by DIC Corporation) Cresol novolac epoxy resin), "Epiclon (registered trademark) 840S" (trade name, manufactured by DIC Corporation, liquid bisphenol A epoxy resin), and the like.

The epoxy equivalent of the epoxy resin is preferably 150 to 500 g / eq, more preferably 170 to 400 g / eq, and more preferably 180 to 300 g / eq from the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and excellent adhesion with the conductor layer. More preferred is eq.
Here, an epoxy equivalent means the mass (g / eq) of the epoxy resin per epoxy group which an epoxy resin has, and can be measured according to the method prescribed | regulated to JISK7236.

The content of the thermosetting resin (A) in the resin composition of the present invention is 3 to 30 with respect to 100 parts by mass in terms of solid content of the resin composition from the viewpoint of smear removability, dielectric loss tangent and heat resistance. A mass part is preferable, 4-20 mass parts is more preferable, 5-15 mass parts is more preferable, 6-12 mass parts is especially preferable.
Here, in the present specification, “solid content conversion” means that only non-volatile components excluding volatile components such as organic solvents are used as a standard. That is, 100 parts by mass in terms of solid content means equivalent to 100 parts by mass of nonvolatile matter.
The content of the epoxy resin in the resin composition of the present invention is the same as the preferable content of the (A) thermosetting resin.

<(B) Inorganic filler>
The resin composition of the present invention contains (B) 55 to 90% by volume of the inorganic filler.
When the content of the inorganic filler (B) is 55% by volume or more, the adhesion to the conductor layer can be enhanced while the low thermal expansion is enhanced. Further, when the content of the (B) inorganic filler is 90% by volume or less, good embedding in a wiring pattern and good adhesion with a conductor layer can be obtained.
From the above viewpoint, the content of the (B) inorganic filler in the resin composition of the present invention is preferably 56 to 80% by volume, more preferably 57 to 70% by volume, and still more preferably 58 to 65% by volume.

(B) The inorganic filler contains (B1) nanofiller and (B2) spherical filler having an average particle diameter larger than the (B1) nanofiller, and in the resin composition for interlayer insulating layer The content of the B1) nanofiller is 0.3 to 2% by volume.
(B) The inorganic filler may contain other inorganic fillers other than (B1) nanofiller and (B2) spherical filler, but (B1) nanofiller and (B2) inorganic filler other than spherical filler It may be one containing no material.
80 mass% or more is preferable, as for the total content of (B1) nano filler and (B2) spherical filler in (B) inorganic filler, 90 mass% or more is more preferable, 95 mass% or more is more preferable, 98 Mass% or more is especially preferable, and 100 mass% may be sufficient.

((B1) Nano filler)
In the present invention, "nanofiller" refers to a filler having an average particle size of less than 200 nm. Examples of the (B1) nanofiller include silica (nanosilica), alumina, titanium oxide and the like having an average particle size of less than 200 nm, and silica (nanosilica) is preferable in terms of further reducing the thermal expansion coefficient. Examples of the silica include spherical silica, amorphous silica, fused silica, crystalline silica, synthetic silica and the like.
The (B1) nanofiller is preferably spherical in order to improve the dispersibility in the resin composition and to obtain good adhesion with the conductor layer.

150 nm or less is preferable, as for the average particle diameter of (B1) nano filler, 100 nm or less is more preferable, and 60 nm or less is more preferable. When the average particle diameter of the (B1) nanofiller is in the above range, (B1) formation of a fine anchor formed by falling off of the nanofiller during wet roughening becomes appropriate and adhesion to the conductor layer is enhanced It becomes possible. In addition, from the viewpoint of handleability and the like, the average particle diameter of the (B1) nanofiller is preferably 4 nm or more, more preferably 6 nm or more, and still more preferably 8 nm or more.
The average particle diameter means volume average particle diameter, and when the cumulative frequency distribution curve by particle diameter is determined with the total volume of particles as 100%, the particle diameter at a point corresponding to 50% volume, It can measure with the particle size distribution measuring device etc. which used the laser diffraction scattering method. Moreover, the average particle diameter of the nanofiller means an average primary particle diameter.

A commercial item may be used for the (B1) nano filler. For example, commercially available nanofillers having an average particle size of 100 nm or less include “AEROSIL R972” and “AEROSIL R202” (trade names) manufactured by Nippon Aerosil Co., Ltd., “PL-1” manufactured by Sakai Chemical Industry Co., Ltd. Trade name, specific surface area 181 m ² / g) and “PL-7” (trade name, specific surface area 36 m ² / g), “AL-A06” (trade name, specific surface area 55 m ² / g) manufactured by CIK Nanotech Co., Ltd. "ADMA NANO" series (having an average particle size of 10 nm and a specific surface area of 300 m ² / g, an average particle size of 50 nm and a specific surface area of 60 m ² / g, and an average particle size of 100 nm and a specific surface area Is 30 m ² / g) and the like.

  (B1) The nanofiller may be surface-treated or may be surface-treated with a surface treatment agent such as a silane coupling agent from the viewpoint of improving moisture resistance, and the dispersibility is improved. It may be treated to be hydrophobic in order to As a silane coupling agent, a phenyl silane coupling agent, an aminosilane coupling agent, a vinyl silane coupling agent, an epoxy silane coupling agent etc. are mentioned.

  The content of the (B1) nanofiller in the resin composition of the present invention is 0.3 to 2% by volume, preferably 0.5 to 1.5% by volume, and 0.6 to 1.3% by volume. More preferable. When the content of the (B1) nanofiller is equal to or more than the above lower limit value, the (B1) nanofiller is dropped and the fine anchor formed during wet roughening becomes appropriate, and the adhesion with the conductor layer is remarkable. It is possible to enhance. In addition, if the content of the (B1) nanofiller is less than or equal to the above upper limit value, the (B1) nanofiller is prevented from becoming too brittle and the resin layer itself becomes brittle, and (B1) nanofiller addition The effect of improving the adhesion with the conductor layer can be maintained favorably. Furthermore, resin flowability can also be improved as content of the (B1) nano filler is the said range.

((B2) spherical filler)
The (B2) spherical filler is a spherical filler having a larger average particle size than the (B1) nanofiller. The resin composition of the present invention can improve the low thermal expansion by containing the (B2) spherical filler. Moreover, when the shape is spherical, the fluidity (pattern embedding property) at the time of laminating the obtained resin film also becomes excellent.
In the present specification, "spherical" includes substantially spherical shapes such as a spherical shape and an elliptical shape, and those having irregularities on the surface thereof. The aspect ratio (long diameter / short diameter) of the spherical filler is, for example, preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.2 or less. The aspect ratio is determined, for example, by observing the shapes of arbitrary 50 particles using a scanning electron microscope (SEM), measuring the major axis and minor axis of these particles, and averaging the aspect ratios. Can.

(B2) As the spherical filler, silica (spherical silica), alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, which is spherical Aluminum borate, barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like can be mentioned. Among these, silica (spherical silica) is preferable because it is inexpensive.
(B2) A spherical filler may be used individually by 1 type, and may use 2 or more types together.

  The average particle diameter of the (B2) spherical filler is larger than that of the (B1) nanofiller, and is preferably 0.25 to 3 μm from the viewpoint of good circuit board embeddability and insulation reliability between layers and wires, 0.3-2 micrometers is more preferable, 0.35-1 micrometer is further more preferable, 0.4-0.8 micrometer is especially preferable.

  (B2) A spherical filler may use a commercial item. As a commercially available (B2) spherical filler, spherical silica, "SO-C1" (average particle diameter: 0.25 μm), "SO-C2" (average particle diameter: 0.5 μm) manufactured by Admatex Co., Ltd. ), “SO-C3” (average particle size: 0.9 μm), “SO-C5” (average particle size: 1.6 μm), “SO-C6” (average particle size: 2.2 μm) (all, all) Trade name) etc.

  The spherical filler (B2) may be surface-treated with a surface treatment agent such as the above-mentioned silane coupling agent from the viewpoint of improving the moisture resistance. The silane coupling agent is preferably one that is surface-treated with an aminosilane coupling agent, from the viewpoint of enhancing the uniformity of the resin surface after wet roughening the interlayer insulating layer obtained.

  The (B1) nanofiller and (B2) spherical filler may be used in the form of a slurry previously dispersed in a solvent.

  54-88 volume% is preferable, as for content of the (B2) spherical filler in the resin composition of this invention, 55-80 volume% is more preferable, 56-70 volume% is more preferable, 58-65 volume% is more preferable. Particularly preferred. (B2) When the content of the spherical filler is 54% by volume or more, good low thermal expansion and high frequency characteristics tend to be obtained, and when it is 88% by volume or less, good embedding in a wiring pattern and There is a tendency for good adhesion with the conductor layer to be obtained.

  The resin composition of the present invention preferably further contains one or more selected from the group consisting of (C) curing agent, (D) phenoxy resin, and (E) curing accelerator.

<(C) Hardening agent>
The curing agent (C) is not particularly limited, and examples of curing agents for epoxy resins include active ester curing agents, phenol resins, acid anhydrides, amines, hydrazides and the like. Among these, active ester curing agents and phenol resins are preferable from the viewpoint of mechanical properties, curing time and dielectric properties of the interlayer insulating layer to be obtained.
The curing agent (C) may be used alone or in combination of two or more.

(Active ester curing agent)
The active ester curing agent used as the curing agent (C) functions as a curing agent for the epoxy resin, and is not particularly limited as long as it has an active ester group.
Compounds having a highly reactive ester group such as phenol esters, thiophenol esters, N-hydroxyamine esters, and ester compounds of heterocyclic hydroxys as an active ester curing agent and having a curing action of an epoxy resin Etc. can be used.

The active ester curing agent is preferably a compound having two or more active ester groups in one molecule, and two in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group. The aromatic compound having the above-mentioned active ester group is more preferable, and is an aromatic compound obtained from a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group, and More preferred are aromatic compounds having two or more ester groups in the molecule of the aromatic compound. The active ester curing agent may also contain a linear or multibranched polymer.
If the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the (A) thermosetting resin can be increased, and it has an aromatic ring. If it is a compound, heat resistance can be made high. In particular, from the viewpoint of heat resistance and the like, the active ester curing agent is preferably an active ester compound obtained from a carboxylic acid compound and a phenol compound or a naphthol compound.

Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Among these, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable.
Examples of thiocarboxylic acid compounds include thioacetic acid and thiobenzoic acid.

As a phenol compound or naphthol compound, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenol phthalin, 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, dihydroxy benzophenone, trihydroxy benzophenone, tetrahydroxy benzophenone, phloroglucin, benzenetriol And dicyclopentadienyl diphenol, phenol novolac and the like. Among these, from the viewpoint of heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak are preferable, and dicyclopentadienyl diphenol and phenol novolak are More preferred is dicyclopentadienyl diphenol.
Examples of the thiol compound include benzene dithiol, triazine dithiol and the like.

As the active ester curing agent, an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available product may be used.
Commercially available active ester curing agents include those having a dicyclopentadienyl diphenol structure, acetylated products of phenol novolac, benzoylated products of phenol novolac, etc. Among these, dicyclopentadienyl diphenol structure Those containing are preferred. Specifically, “EXB9451”, “EXB9460”, “EXB9460S-65T”, and “HPC-8000-65T” (all trade names, manufactured by DIC Corporation, esters) as having a dicyclopentadienyldiphenol structure Base equivalent 223 g / eq), acetylated phenol novolak “DC 808” (trade name, manufactured by Mitsubishi Chemical Co., Ltd., ester equivalent 149 g / eq), phenol novolac benzoyl compound “YLH1026” (trade name, Mitsubishi Chemical Corporation stock An ester group equivalent of 200 g / eq) and the like can be mentioned.

  The active ester curing agent is not particularly limited, and can be produced by a known method. Specifically, it can be obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound.

  When the resin composition of the present invention contains an active ester curing agent, the content thereof is 100 parts by mass in terms of the solid content of the resin composition from the viewpoint of the mechanical properties, curing time and dielectric properties of the interlayer insulating layer obtained. On the other hand, 2 to 30 parts by mass is preferable, 3 to 25 parts by mass is more preferable, and 4 to 20 parts by mass is more preferable.

(Phenol resin)
(C) As a phenol resin used as a hardening | curing agent, the phenol resin which has a 2 or more phenolic hydroxyl group in 1 molecule is preferable. Specifically, compounds having two phenolic hydroxyl groups in one molecule, such as resorcin, catechol, bisphenol A, bisphenol F and substituted or unsubstituted biphenol; aralkyl type phenol resin; dicyclopentadiene type phenol resin; Novolac type phenolic resin such as phenyl novolac resin, cresol novolac resin, bisphenol A novolac resin, aminotriazine modified novolac type phenolic resin; Resole type phenolic resin; copolymer type of benzaldehyde type phenol and aralkyl type phenol Phenolic resin; p-xylylene and / or m-xylylene modified phenolic resin; melamine modified phenolic resin; terpene modified phenolic resin; dicyclopentadiene type naphth Lumpur resins; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; and biphenyl type phenolic resins. Among these, from the viewpoint of improving the reliability, novolac type phenol resins are preferable, and cresol novolac resins are more preferable.

  When the resin composition of the present invention contains a phenol resin, the content thereof is 100 parts by mass relative to the solid content of the resin composition from the viewpoint of mechanical properties, curing time and dielectric properties of the interlayer insulating layer obtained. 2-30 mass parts is preferable, 3-15 mass parts is more preferable, and 4-10 mass parts is further more preferable.

<(D) phenoxy resin>
The resin composition of the present invention preferably contains (D) a phenoxy resin. (D) By containing a phenoxy resin, the adhesion between the obtained interlayer insulating layer and the conductor layer tends to be improved, and the roughened shape of the surface of the interlayer insulating layer tends to be small and dense. . In addition, when the conductor layer is formed on the interlayer insulating layer using the electroless plating method, the occurrence of plating blisters is suppressed, and the adhesion strength between the interlayer insulating layer and the solder resist tends to be improved.
The phenoxy resin (D) may be used alone or in combination of two or more.

Here, “phenoxy resin” is a general term for a polymer whose main chain is a polyaddition structure of aromatic diol and aromatic diglycidyl ether, and in the present specification, the weight average molecular weight is 10,000. Point to the above. When the polymer whose main chain is a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether has an epoxy group, one having a weight average molecular weight of 10,000 or more is classified as (D) phenoxy resin, and the weight is Those having an average molecular weight of less than 10,000 are classified as epoxy resins.
The weight average molecular weight of the phenoxy resin (D) is preferably 10,000 to 100,000 from the viewpoint of improving the solubility in an organic solvent and the mechanical strength and chemical resistance of the interlayer insulating layer. When the weight average molecular weight is in the above range, the occurrence of blisters in the conductor layer tends to be suppressed.
The weight average molecular weight is measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a standard polystyrene calibration curve.

(D) As the phenoxy resin, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol AF skeleton, bisphenol trimethylcyclohexane skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, Those having one or more types of skeletons selected from naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, trimethylcyclohexane skeleton, copolymer skeleton of styrene and glycidyl methacrylate are mentioned. Among them, phenoxy having a biphenyl skeleton from the viewpoint of improving the chemical resistance of the interlayer insulating layer and from the viewpoint of facilitating the interlayer insulating layer to have appropriate irregularities with an oxidizing agent in roughening, desmearing treatment, etc. Resins are preferred.
The terminal of the (D) phenoxy resin may be either a phenolic hydroxyl group or an epoxy group.

  A commercial item may be used as phenoxy resin (D). As commercially available (D) phenoxy resins, bisphenol AF skeleton-containing phenoxy resins “YL 7383” and “YL 7384”, and bisphenol A skeleton-containing phenoxy resins “1256” and “4250” (trade names, Mitsubishi Chemical Corporation) "YP-50" (trade name, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), "YX8100" which is a bisphenol S skeleton-containing phenoxy resin, "YX6954" which is a bisphenol acetophenone skeleton-containing phenoxy resin Trade name, manufactured by Mitsubishi Chemical Corporation, "FX-293" (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) which is a fluorene skeleton-containing phenoxy resin, "YL7213" (merchandise, which is a bisphenol trimethylcyclohexane skeleton-containing phenoxy resin Name, manufactured by Mitsubishi Chemical Corporation , Other, “FX-280” (trade name, manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), “YL7553”, “YL6794”, “YL7290”, “YL7482” (trade names, manufactured by Mitsubishi Chemical Corp.), etc. Can be mentioned.

  (D) The phenoxy resin is, for example, a bisphenol compound having a trimethylcyclohexane structure or a bisphenol compound having a terpene structure and a bifunctional epoxy resin as raw materials, according to a known process for producing phenoxy resin and epoxy group and phenolic hydroxyl group It can be produced by reacting in the range of the equivalent ratio of about 1: 0.9 to 1: 1.1.

  When the resin composition of the present invention contains (D) phenoxy resin, the content thereof is preferably 0.5 to 20 parts by mass, and 1 to 10 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition. Part is more preferred. When the content of the phenoxy resin (D) is 0.5 parts by mass or more, sufficient flexibility is obtained, and the handling property is excellent, and the adhesion to the conductor layer formed by plating tends to be excellent. When the amount is 20 parts by mass or less, sufficient fluidity can be obtained during lamination, and an appropriate roughness tends to be obtained.

<(E) Hardening accelerator>
The resin composition of the present invention preferably contains (E) a curing accelerator from the viewpoint of enabling curing at a low temperature and in a short time.
(E) As a curing accelerator, imidazole compounds such as 2-phenylimidazole, 4-dimethylaminopyridine, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate; triphenylphosphine etc. Organophosphorus compounds; onium salts such as phosphonium borate; amines such as 1,8-diazabicycloundecene; 3- (3,4-dichlorophenyl) -1,1-dimethyl urea, 4-dimethylaminopyridine and the like It can be mentioned.
The curing accelerator (E) may be used alone or in combination of two or more.

  When the resin composition of the present invention contains (E) a curing accelerator, its content is preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass on a solid content basis of the resin composition, 0 The amount is more preferably 0.015 to 0.4 parts by mass, further preferably 0.02 to 0.3 parts by mass. (E) A sufficient curing rate is obtained when the content of the curing accelerator is the above lower limit value, and the flatness of the resin layer on the inner layer pattern, the interlayer insulating layer obtained by curing with a support. Excellent in the appearance of In addition, when the content of the (E) curing accelerator is less than or equal to the above upper limit value, the handling and embedding properties of the obtained resin film are excellent.

<Other ingredients>
The resin composition of this invention may contain components other than said each component in the range which does not inhibit the effect of this invention. Examples of the other components include thermosetting resins other than the above-described components, thermoplastic resins, additives, organic solvents and the like.

(Additive)
Additives include flame retardants such as inorganic flame retardants and resin flame retardants; thickeners such as orben and benton; adhesion imparting agents such as imidazoles, thiazoles, triazoles, and silane coupling agents; flame retardants; rubber particles And colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black and the like.

(Organic solvent)
The resin composition of the present invention may be used as a varnish-like resin composition containing an organic solvent (hereinafter also referred to as "resin varnish") from the viewpoint of easy handling and the ease of forming a resin film. Good.
Organic solvents include acetone, methyl ethyl ketone (hereinafter, also referred to as "MEK"), methyl isobutyl ketone, ketone solvents such as cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetic acid such as carbitol acetate Ester solvents; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of solubility, ketone solvents are preferable, and MEK and methyl isobutyl ketone are more preferable.

  The resin composition of this invention can be manufactured by mixing said each component. As the mixing method, known methods can be applied, and known kneading and dispersion methods such as a kneader, ball mill, bead mill, triple roll, nanomizer, etc. can be applied.

[Resin film for interlayer insulation layer]
The resin film for interlayer insulation layer (hereinafter, also simply referred to as “resin film”) of the present invention comprises a support and a resin composition layer for interlayer insulation layer (hereinafter, also simply referred to as “resin composition layer”). In the resin film for interlayer insulating layer, the resin composition layer for interlayer insulating layer is a layer formed by forming the resin composition for interlayer insulating layer of the present invention.
The resin film of the present invention can be used for a buildup type multilayer printed wiring board, and can form a conductor layer having high adhesive strength on a smooth interlayer insulating layer. In the present invention, “smooth” means that the surface roughness Ra is less than 0.3 μm.

<Resin composition layer for interlayer insulating layer>
The resin composition layer is a layer formed by layering the resin composition of the present invention, and in the case of producing a multilayer printed wiring board using the resin film of the present invention, the resin composition layer is in direct contact with the circuit board during lamination, It is a layer that melts and flows in the wiring pattern to fill the circuit board. Also, when through holes, via holes, etc. exist in the circuit board, they flow into them and play a role of filling the inside of the holes.
The resin composition layer is obtained by layering the resin composition of the present invention. The layer formation can be performed, for example, by dissolving and / or dispersing the resin composition of the present invention in the organic solvent to form a resin varnish, and then applying and drying it.

  The thickness of the resin composition layer can be appropriately determined according to the desired performance. For example, since the thickness of the conductor layer formed on the printed wiring board is usually 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm while having a thickness equal to or greater than that of the conductor layer. 15 to 80 μm is more preferable, and 20 to 50 μm is more preferable. In addition, from the viewpoint of thinning the multilayer printed wiring board, the thickness of the resin composition layer is preferably 1 to 50 μm, and more preferably 10 to 45 μm.

<Support>
Although it does not specifically limit as a support body used for the resin film of this invention, An organic resin film, metal foil, a release paper etc. are mentioned.
Examples of the material of the organic resin film include polyolefins such as polyethylene and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter, also referred to as "PET") and polyethylene naphthalate; polycarbonates and polyimides. Among these, PET is preferable in terms of cost and handling.
As metal foil, copper foil, aluminum foil, etc. are mentioned. In the case of using a copper foil as the support, the copper foil can be used as it is as a conductor layer to form a circuit. In this case, rolled copper, electrolytic copper foil or the like can be used as the copper foil. Also, the thickness of the copper foil is not particularly limited, but for example, one having a thickness of 2 to 36 μm can be used. In the case of using a thin copper foil, a copper foil with a carrier may be used from the viewpoint of improving the workability.

The support may be subjected to matting treatment, corona treatment, release treatment and the like.
The thickness of the support is usually 10 to 150 μm, preferably 25 to 50 μm.
When the thickness of the support is 10 μm or more, the handling becomes easy. On the other hand, since the support is usually peeled off or removed finally, the thickness is preferably 75 μm or less from the viewpoint of energy saving and the like.
The support is preferably a polyethylene terephthalate film having a thickness of 75 μm or less from the viewpoint of cost and handling.

<Protective film>
The resin film of the present invention may have a protective film. The protective film is provided on the side opposite to the side on which the support of the resin film of the present invention is provided, and is used for the purpose of preventing adhesion and scratching of foreign matter and the like to the resin film. . The protective film is peeled off before laminating the resin film of the present invention on a circuit board or the like by lamination, heat press or the like.
As a protective film, the material similar to a support body can be used, for example. The thickness of the protective film is, for example, 1 to 40 μm.

<Production method of resin film>
Examples of the method for producing the resin film of the present invention include a method in which a varnish-like resin composition of the present invention is coated on a support and then dried to form a resin composition layer.
As a method of coating a resin composition, the method of coating using well-known coating apparatuses, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, is mentioned. The coating apparatus may be appropriately selected according to the target film thickness.

As a drying condition after applying the resin composition of the present invention, a condition in which the content of the organic solvent in the resin film after drying is 10% by mass or less is preferable, and a condition in which the content is 5% by mass or less is more preferable. Since the drying conditions also affect the temperature-melt viscosity curve of the resin composition of the present invention, it is preferable to set the drying conditions so as to satisfy the handleability of the film.
Although the specific drying conditions vary depending on the amount and type of the organic solvent in the resin varnish, for example, in the case of a resin varnish containing 30 to 80% by mass of the organic solvent, it is about 50 minutes at 50 ° C for 3 to 10 minutes. The resin film can be formed by drying.
As the drying conditions, it is preferable to appropriately set suitable drying conditions by simple experiments.
Moreover, the resin film can be wound up in a roll, and can be stored and stored.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present invention contains one or more cured products selected from the group consisting of the resin composition of the present invention and the resin composition layer of the resin film of the present invention.
The multilayer printed wiring board of the present invention can be produced, for example, by laminating the resin film of the present invention on a circuit board. Specifically, the following steps (1) to (6) [wherein the step (3) is optional. ] And the support may be peeled off or removed after step (1), (2) or (3).

(1) A step of laminating the resin film of the present invention on one side or both sides of a circuit board [hereinafter referred to as a laminating step (1)].
(2) A step of thermally curing the resin composition layer of the laminated resin film to form an insulating layer [hereinafter, referred to as insulating layer forming step (2)].
(3) A step of drilling a circuit board on which an insulating layer is formed [hereinafter referred to as a drilling step (3)].
(4) Step of roughening the surface of the insulating layer with an oxidizing agent [hereinafter referred to as roughening step (4)].
(5) A step of forming a conductor layer on the surface of the roughened insulating layer by plating [hereinafter referred to as a conductor layer forming step (5)].
(6) Step of forming a circuit on a conductor layer [hereinafter referred to as circuit forming step (6)].

  The laminating step (1) is a step of laminating the resin film of the present invention on one side or both sides of a circuit board using a vacuum laminator or the like. As a vacuum laminator, a commercially available vacuum laminator can be used. Commercially available vacuum laminators include vacuum applicators manufactured by Nichigo-Morton Co., Ltd., vacuum pressure type laminators manufactured by Meitoki Co., Ltd., roll type dry coaters manufactured by Hitachi Ltd., vacuums manufactured by Hitachi Chemical Electronics Co., Ltd. Laminator etc. are mentioned.

When a protective film is provided on the resin film, after peeling off or removing the protective film, the resin film of the resin film is pressed against the circuit substrate while being pressurized and heated so that the resin composition layer of the resin film is in contact with the circuit substrate. Can be laminated.
The laminate is prepared, for example, by preheating the resin film and the circuit board as required, and then, the pressure bonding temperature (lamination temperature) is 60 to 140 ° C., and the pressure bonding pressure is 0.1 to 1.1 MPa (9. It can be carried out under a reduced pressure of 8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ) and an air pressure of 20 mmHg (26.7 hPa) or less. Also, the method of lamination may be a batch system or a continuous system with a roll.

In the insulating layer forming step (2), first, the resin film laminated on the circuit board in the laminating step (1) is cooled to around room temperature.
In the case of peeling the support, after peeling, the resin composition layer of the resin film laminated on the circuit board is cured by heating to form an insulating layer, that is, an insulating layer to be an "interlayer insulating layer" later.
The conditions for heat curing are selected in the range of 150 to 220 ° C. for 20 to 120 minutes, and more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes. When a support subjected to release treatment is used, the support may be peeled off after heat curing.
The heat curing may be divided into two or more steps, and for example, after heating for about 30 minutes at 150 ° C. or less, the material may be cured by heating at 160 to 200 ° C. for 20 to 120 minutes.

After forming the insulating layer by the above method, if necessary, it may go through a drilling process (3).
The drilling step (3) is a step of drilling holes in the circuit board and the formed insulating layer by a method such as drilling, laser, plasma, or a combination thereof to form via holes, through holes, and the like. As a laser, a carbon dioxide gas laser, a YAG laser, a UV laser, an excimer laser or the like is used.
The support may be peeled off after this step (3). In recent years, in order to strengthen the strength of the laser and perform drilling in a short time, it is possible to perform drilling using a carbon dioxide gas laser in a state where a support is attached, and peel the support film after drilling. .

In the roughening treatment step (4), the surface of the insulating layer is roughened with an oxidizing agent. In the case where via holes, through holes and the like are formed in the insulating layer and the circuit board, so-called "smear" generated when forming these may be removed by an oxidizing agent. The roughening treatment and the removal of the smear can be performed simultaneously.
It is preferable that the manufacturing method of the multilayer printed wiring board of this invention performs a wet roughening process.
Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate etc.), dichromate, ozone, hydrogen peroxide, sulfuric acid, nitric acid and the like. Among these, alkaline permanganic acid solutions (eg, potassium permanganate, sodium permanganate hydroxide), which is an oxidizing agent generally used for roughening the insulating layer in the production of a multilayer printed wiring board by a build-up method Sodium aqueous solution can be used.
The roughening treatment forms an uneven anchor on the surface of the insulating layer.
In the method for producing a multilayer printed wiring board of the present invention, the weight reduction amount of the cured product of the resin composition for interlayer insulating layers in the wet roughening treatment is preferably 1.3 g / m ² or less, and 1.2 g / m ^2. m ² or less is more preferable, and 1.1 g / m ² or less is more preferable. When the weight loss is 1.3 g / m ² or less, the resin layer is sufficiently left on the roughened surface after desmearing, and the peel strength improvement effect of the (B1) nanofiller is significantly exhibited. On the other hand, from the viewpoint of forming an appropriate anchor, the weight reduction amount of the cured product of the resin composition for interlayer insulating layer in the wet roughening treatment may be 0.5 g / m ² or more, 0.6 g / M ² or more may be sufficient.
The weight loss of the cured product in the wet roughening treatment can be measured by the method described in the examples.

In the conductor layer forming step (5), the conductor layer is formed by plating on the surface of the insulating layer which has been roughened and on which the anchors of asperities are formed.
The plating method may, for example, be an electroless plating method or an electrolytic plating method. The metal for plating is not particularly limited as long as it can be used for plating.
Alternatively, a plating resist having a pattern reverse to that of the conductor layer (wiring pattern) may be formed first, and then the conductor layer (wiring pattern) may be formed only by electroless plating.
After the formation of the conductor layer, annealing may be performed, for example, at 150 to 200 ° C. for 20 to 90 minutes. The adhesion between the interlayer insulating layer and the conductor layer tends to be further improved and stabilized by the annealing treatment.
In the circuit formation step (6), known methods such as a subtractive method and a semiadditive process (SAP: SemiAdditive Process) can be applied as a method for patterning the conductor layer.
The surface of the produced conductor layer may be roughened from the viewpoint of improving the adhesion to the resin in contact with the conductor layer.

The circuit board used for the multilayer printed wiring board of the present invention is not particularly limited, but on one side or both sides of a substrate such as glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, The thing in which the patterned conductor layer (circuit) was formed is mentioned.
In addition, a multilayer printed wiring board having conductor layers (circuits) in which conductor layers and insulating layers are alternately formed and patterned on one side or both sides, the resin film of the present invention on one side or both sides of the circuit board Those having a formed interlayer insulating layer and having a conductor layer (circuit) patterned on one side or both sides thereof, pattern processed on one side or both sides of a cured product formed by laminating and curing the resin film of the present invention A circuit board includes one having a conductive layer (circuit).
The surface of the conductor layer of the circuit board may be subjected to roughening treatment such as blackening treatment from the viewpoint of adhesion of the interlayer insulating layer to the circuit board.

[Semiconductor package]
The semiconductor package of the present invention is obtained by mounting a semiconductor on the multilayer printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor chip, a memory and the like at a predetermined position of the multilayer printed wiring board of the present invention by a known method.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[Production of resin film for interlayer insulating layer]
Examples 1 to 10, Comparative Examples 1 to 3, Reference Example 1
The resin varnish was prepared by blending according to the composition shown in Table 1 (unit: parts by mass, but the solid content equivalent is shown in the case of a solution or dispersion), and subjected to mixing and bead mill dispersion treatment. The resin varnish is coated on a PET film as a support (trade name: SY-RX manufactured by Toray Film Processing Co., Ltd., thickness: 38 μm), and then dried to obtain a resin composition layer on the support. A resin film was produced. In addition, coating thickness was adjusted so that the thickness of the resin composition layer after drying might be 40 micrometers, and drying was performed so that the residual solvent in a resin composition layer might be 3.0 mass%. After drying, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: NF-13, thickness: 25 μm) was laminated as a protective film on the resin composition layer side, and the obtained film was wound into a roll.
The resin film obtained above was evaluated by the following method. The results are shown in Table 1.

[Weight loss after desmear treatment]
The resin film obtained in each example was cut into 200 mm squares, and then the protective film was peeled off, and the resin composition layer was disposed so as to face the circuit surface of the printed wiring board, and then lamination was performed.
The printed wiring board is a copper-clad laminate “MCL-E-679FG” (trade name, manufactured by Hitachi Chemical Co., Ltd.) having a 35 μm-thick copper layer, and any remaining copper rate of 0 to 95% by a subtractive method The circuit processed was used.
The laminate was vacuumed at 110 ° C. for 30 seconds using a vacuum pressure type laminator “MVLP-500 / 600 IIA” (trade name, manufactured by Name Machine Co., Ltd.) and then pressurized at 0.5 MPa for 30 seconds. Thereafter, hot pressing was performed at 110 ° C. for 60 seconds at 0.5 MPa. Next, after cooling to room temperature, curing was performed in an explosion-proof drier at 130 ° C. for 20 minutes and then at 180 ° C. for 40 minutes with the support attached, to prepare a cured substrate.
The obtained cured substrate was cut into 60 mm × 40 mm and dried at 105 ° C. for 30 minutes, and then the weight was measured, and the weight measured here was taken as “Weight A”.
Then, the cured substrate whose weight was measured was subjected to a soaking treatment in a swelling solution “Swelling Dip Security Gart P” (trade name) heated to 70 ° C. for 10 minutes. Next, it was immersed in a roughening solution “Concentrate Compact CP” (trade name) heated to 80 ° C. for 20 minutes, and was subsequently heated to 40 ° C., and a neutralization solution “Reduction Security P500” (trade name) Soak for 5 minutes to neutralize. Thus, a desmear-treated substrate was obtained. The above-mentioned swelling solution, roughening solution and neutralization solution were all manufactured by Atotech Japan Co., Ltd.
The resulting desmear-treated substrate was dried at 105 ° C. for 30 minutes, and then its weight was measured. The weight measured here was taken as “Weight B”.
From the weight A and weight B obtained above, the weight loss in the desmear treatment was calculated based on the following equation.
Weight loss (g / m ² ) = [weight A (g) -weight B (g)] / [2 * 0.04 (m) * 0.06 (m)]

[Surface roughness after desmearing (Ra)
The arithmetic mean roughness (Ra) of the resin surface of the above-described desmear-treated substrate is measured three times using a non-contact surface roughness meter (trade name: Contour GT-X manufactured by Bruker), and the mean value is desmeared It was set as the surface roughness after.

[Peel strength (adhesion to conductor layer)]
The desmear-treated substrate obtained above is dipped in “cleaner security gant 902” (trade name) at 60 ° C. for 5 minutes as a cleaner, and then, as a pre-dip liquid, “pre-dip neogant B” (trade name) For 2 minutes at 25 ° C, 5 minutes at 40 ° C as "Activator Neo Gant 834" (trade name) as a seeder, 5 minutes at 30 ° C as "Reducer Neo Gant WA" (trade name) as a reducer An immersion treatment was carried out at 30 ° C. for 30 minutes in “MSK-DK” (trade name) to form an electroless plated layer of 200 to 250 nm. Furthermore, the electroplating thickness of 25-30 micrometers was formed with the current density of ² A / dm <2> with a copper sulfate plating bath. The above-mentioned cleaner, pre-dip solution, seeder, reducer and electroless plating were all manufactured by Atotech Japan Co., Ltd.
Next, the substrate on which the electroplating layer was formed was heat treated at 190 ° C. for 90 minutes, and an acrylic tape having a width of 10 mm was attached to the treated plated surface, and then the plated copper was etched away with an aqueous ammonium persulfate solution. After etching, the acrylic tape was peeled off to obtain a substrate for peel strength measurement having a copper layer of 10 mm width.
One end of the copper layer of the peel strength measurement substrate is peeled off at the interface between the copper layer and the interlayer insulating layer and held with a clamp, using a small desktop tester (trade name: EZT Test, manufactured by Shimadzu Corporation) Peel strength was measured in accordance with JIS C 6481.

Thermal expansion coefficient (CTE)
The resin film obtained in each example was thermally cured by heating at 190 ° C. for 90 minutes, and then the support was peeled to obtain a sheet-like cured product. About the said hardened | cured material, the average thermal expansion coefficient (ppm / (degreeC) in the range of 0-50 degreeC was measured using the thermomechanical analyzer (made by TAIntruments, brand name: TMA-2940).

Details of each material shown in Table 1 are shown below.
[(A) thermosetting resin]
・ JER 828US: Bisphenol A epoxy resin (Mitsubishi Chemical Co., Ltd., trade name, solid concentration 100% by mass, epoxy equivalent: 184 to 194 g / eq)
NC-3000-H: biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name, solid content concentration 100 mass%, epoxy equivalent: 288 g / eq)
・ N673: Cresol novolac epoxy resin (manufactured by DIC Corporation, epoxy equivalent: 211 g / eq)
[(B1) nano filler]
Nano filler 1: Nano silica “Adma Nano φ10 nm” (trade name, manufactured by Admatex Co., Ltd., average particle diameter: 10 nm) treated with a phenylsilane coupling agent (solid content concentration 100 mass%)
Nano-filler 2: The surface of the above-mentioned "adma nano φ 10 nm" is treated with a vinylsilane coupling agent (solid content concentration 100% by mass)
Nano filler 3: the surface of the above "Adoma nano φ 10 nm" treated with an epoxy silane coupling agent (solid content concentration 100% by mass)
-Nano filler 4: The above "Adma nano φ 10 nm" (without surface treatment)
Nano filler 5: Nano silica “Adma Nano φ 50 nm” (trade name, manufactured by Admatex Co., Ltd., average particle diameter: 50 nm) treated with a phenylsilane coupling agent (solid content concentration 100 mass%)
Nano filler 6: fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name, average particle diameter: 20 nm, solid content concentration 100 mass%)
[(B2) spherical filler]
· A surface of spherical silica "SO-C2" (trade name, manufactured by Admatex Co., Ltd., average particle diameter: 0.5 μm) treated with an aminosilane coupling agent, and further dispersed in MEK (solids concentration 70 mass%)
[(C) curing agent]
HPC-8000-65T: Active ester curing agent (active ester compound containing dicyclopentadiene type diphenol structure) (made by DIC Corporation, trade name, solid content concentration 65 mass%, ester group equivalent: 223 g / mol, toluene cut)
-KA1165: cresol novolac type phenol resin (made by DIC Corporation, trade name, solid content concentration 100 mass%)
[(D) phenoxy resin]
-YX 6954 B30: bisphenol acetophenone skeleton-containing phenoxy resin (Mitsubishi Chemical Co., Ltd., trade name, solid content concentration 30 mass%, MEK cut)
[(E) curing accelerator]
4-DMAP: 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration 100% by mass)
2PZ-CN-PW: 1-cyanoethyl-2-phenylimidazolium trimellitate (manufactured by Shikoku Kasei Kogyo Co., Ltd., solid content concentration 100% by mass)

From Table 1, in the interlayer insulating layers obtained in Examples 1 to 10 using the resin composition of the present invention, the peel strength is significantly improved as compared with Comparative Example 1 in which (B1) nanofiller is not contained. I understand that. Further, Comparative Example 2 in which the content of (B1) nanofiller exceeds 2% by volume, and Comparative Example 3 in which the content of (B1) nanofiller is less than 0.2% by volume all had low peel strength. .
In Reference Example 1 in which the weight loss after desmear treatment exceeded 1.3 g / m ² , the surface roughness increased, and no improvement in peel strength was observed.
The surface SEM photograph of the interlayer insulation layer after the wet roughening process formed in Example 1 in FIGS. 1 and 2 is a surface SEM photograph of the interlayer insulation layer after the wet roughening treatment formed in Comparative Example 1 in FIG. Indicates In any of the SEM photographs, it is clearly confirmed that the spherical filler having a large average particle diameter (B2) is exposed on the surface, but in FIGS. 1 and 2, the resin portion is a drop of the (B1) nanofiller It can be seen that a dense roughened shape is formed due to the like. On the other hand, in FIG. 3 of Comparative Example 1, it can be seen that the resin portion has a smooth shape, and the dense roughened shape as in Example 1 is not formed. From these results, in the interlayer insulating layer formed from the resin composition of the present invention, the peel strength is enhanced because the resin portion has a dense roughened shape even when the inorganic filler is filled in a large amount. As a result, it can be seen that excellent low thermal expansion and adhesion with the conductor layer can be achieved.

  The resin composition of the present invention makes it possible to form an interlayer insulating layer in which the low thermal expansion and the adhesion to the conductor layer are compatible. Therefore, the resin composition of the present invention can be widely used in electronic products such as computers, mobile phones, digital cameras, and televisions; and vehicles such as motorcycles, automobiles, trains, ships, and aircraft.

Claims (14)

A resin composition for an interlayer insulating layer comprising (A) a thermosetting resin and (B) an inorganic filler,
The content of the (B) inorganic filler in the interlayer insulating layer resin composition is 55 to 90% by volume,
(B) The inorganic filler contains (B1) nanofillers and (B2) spherical fillers having an average particle diameter larger than the (B1) nanofillers,
The resin composition for interlayer insulation layers whose content of the (B1) nano filler in the resin composition for interlayer insulation layers is 0.3-2 volume%.   The resin composition for interlayer insulation layers of Claim 1 whose average particle diameter of (B1) nano filler is 150 nm or less.   The resin composition for interlayer insulation layers of Claim 1 or 2 whose content of (B2) spherical filler in the resin composition for interlayer insulation layers is 54 to 88 volume%.   The resin composition for interlayer insulation layers of any one of Claims 1-3 whose (B1) nano filler is a silica.   The resin composition for an interlayer insulating layer according to any one of claims 1 to 4, wherein the (B1) nanofiller is not subjected to a surface treatment or is subjected to a surface treatment with a silane coupling agent. object.   The resin composition for interlayer insulation layers of any one of Claims 1-5 whose average particle diameter of (B2) spherical filler is 0.25-3 micrometers.   The resin composition for interlayer insulation layers of any one of Claims 1-6 whose (B2) spherical filler is spherical silica.   The resin composition for interlayer insulation layers according to any one of claims 1 to 7, wherein the spherical filler (B2) is surface-treated with an aminosilane coupling agent.   It has a support body and a resin composition layer for interlayer insulation layers, and the resin composition layer for interlayer insulation layers forms the resin composition for interlayer insulation layers of any one of Claims 1-8. Resin film for interlayer insulation layer which is   The resin film for interlayer insulation layers of Claim 9 whose said support body is a polyethylene terephthalate film and whose thickness is 75 micrometers or less.   The resin film for interlayer insulation layers of Claim 9 or 10 whose thickness of the said resin composition layer for interlayer insulation layers is 1-50 micrometers.   The resin composition for interlayer insulation layers of any one of Claims 1-8, The resin composition for interlayer insulation layers which the resin film for interlayer insulation layers of any one of Claims 9-11 has A multilayer printed wiring board comprising one or more cured products selected from the group consisting of layers.   The semiconductor package which mounts a semiconductor element in the multilayer printed wiring board of Claim 12. A method of producing a multilayer printed wiring board according to claim 12, comprising the step of wet roughening the cured product, wherein the weight loss of the cured product in the wet roughening step is 1 .3 g / m < ² > or less, the manufacturing method of a multilayer printed wiring board.