JP2019127571A - Resin composition for insulating layer, sheet-like laminated material, multilayer printed wiring board, and semiconductor device - Google Patents

Abstract

To provide a resin composition for an insulating layer which simultaneously achieves excellent low thermal expansion, dielectric characteristics, and smear removability, and to provide a sheet-like laminated material, a multilayer printed wiring board, and a semiconductor device using the resin composition for an insulating layer.SOLUTION: The resin composition for an insulating layer contains (A) a compound having a polybutadiene skeleton, (B) an epoxy resin, (C) an active ester curing agent, and (D) an inorganic filler. The content of the inorganic filler (D) is 50-85 pts.mass based on 100 pts.mass in terms of solid content of the resin composition for an insulating layer. The sheet-like laminated material, the multilayer printed wiring board, and the semiconductor device using the resin composition for an insulating layer are also provided.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for an insulating layer, a sheet-like laminated material, a multilayer printed wiring board, and a semiconductor device.

In recent years, miniaturization and high performance of electronic devices have progressed, and in multilayer printed wiring boards, buildup layers have been multilayered, and miniaturization and densification of wiring have progressed. With the miniaturization and high density of wiring, various performances are also required for the insulating layer of multilayer printed wiring boards.
For example, the buildup layer is required to have a low thermal expansion coefficient because of the demand for reduction of the amount of warpage after semiconductor mounting. As a technique for reducing the coefficient of thermal expansion, a method of highly filling an inorganic filler in a thermosetting resin (for example, a method using 40% by mass or more in a buildup layer as a silica filler) is applied.

  Also, in recent years, in computers and information communication devices, the performance of signals has become increasingly high performance and functionality, and in order to process a large amount of data at high speed, there is a tendency for signals to be handled to have a high frequency. In particular, the radio wave frequency range used for mobile phones, satellite broadcasting, etc. is in the high frequency range of GHz band, and organics used in the high frequency range are used to suppress transmission loss due to high frequency. Materials having low dielectric constants and dielectric dissipation factors are desired.

Patent Document 1 discloses an epoxy resin, an active ester compound, a carbodiimide compound, as a resin composition that provides an insulating layer that is excellent in all of the characteristics of dielectric loss tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength. A resin composition containing a thermoplastic resin and an inorganic filler is disclosed.
Patent Document 2 contains an epoxy resin, an active ester compound, a curing accelerator, and an inorganic filler as a support-containing prepolymer sheet excellent in smear removability and peel strength despite the low linear thermal expansion coefficient. There is disclosed a support-containing prepolymer sheet having a layer.

JP 2016-27097 A JP 2014-69405 A

However, the present inventors, such as the resin compositions disclosed in Patent Documents 1 and 2, do not use carbonic acid in a resin composition that uses an active ester curing agent and a resin composition that is highly filled with an inorganic filler. In via formation by gas laser, the problem that laser processability, smear removability, etc. tend to deteriorate was discovered. This problem tends to be ameliorated by lowering the content of the active ester curing agent, but in that case, there arises a problem that the dielectric loss tangent is increased.
That is, the resin compositions disclosed in Patent Documents 1 and 2 are not sufficiently compatible with all of low thermal expansion, low dielectric loss tangent and smear removability, and there is room for improvement.

  The present invention has been made in view of the above circumstances, and the insulating layer obtained is a resin composition for an insulating layer which is excellent in low thermal expansion, low dielectric loss tangent and smear removability, and the resin composition for the insulating layer. It is an object of the present invention to provide a sheet-like laminated material, a multilayer printed wiring board, and a semiconductor device.

As a result of extensive research to achieve the above object, the present inventors mix a compound having a polybutadiene skeleton in a resin composition for an insulating layer containing an epoxy resin, an active ester curing agent and an inorganic filler. It has been found that the above problem can be solved.
That is, the present invention relates to the following [1] to [14].
[1] A resin composition for an insulating layer, which comprises (A) a compound having a polybutadiene skeleton, (B) an epoxy resin, (C) an active ester curing agent, and (D) an inorganic filler.
The resin composition for insulating layers whose content of the said (D) inorganic filler is 50-85 mass parts with respect to solid content conversion 100 mass parts of this resin composition for insulating layers.
[2] The insulating layer according to the above [1], wherein the content of the component (A) is 0.5 to 5 parts by mass with respect to 100 parts by mass on a solid basis of the resin composition for the insulating layer Resin composition.
[3] The resin composition for an insulating layer according to the above [1] or [2], wherein the component (A) is a compound having a polybutadiene skeleton and an epoxy group.
[4] Any one of the above [1] to [3], wherein the content of the component (B) is 1 to 30 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition for the insulating layer The resin composition for insulating layers as described in 2.
[5] The above [1] to [4], wherein the component (B) is at least one selected from the group consisting of naphthalene type epoxy resins, biphenyl type epoxy resins, naphthol type epoxy resins and bixylenol type epoxy resins ] The resin composition for insulating layers in any one of.
[6] Any one of the above [1] to [5], wherein the content of the component (C) is 1 to 30 parts by mass with respect to 100 parts by mass on a solid basis of the resin composition for the insulating layer The resin composition for insulating layers as described in 2.
[7] Any one of the above [1] to [6], wherein the content of the component (D) is 70 to 80 parts by mass with respect to 100 parts by mass in terms of solid content of the insulating layer resin composition The resin composition for insulating layers as described in 2.
[8] The resin composition for an insulating layer according to any one of the above [1] to [7], wherein the component (D) is silica.
[9] The resin composition for an insulating layer according to any one of the above [1] to [8], wherein the component (D) is surface-treated with a silane coupling agent having an amino group.
[10] Any one of the above [1] to [9], wherein the content of the component (A) is 2 to 20 parts by mass with respect to 100 parts by mass of the resin component in the insulating layer resin composition The resin composition for insulating layers as described in 2.
[11] The resin composition for an insulating layer according to any one of the above [1] to [10], which is used for a buildup layer of a multilayer printed wiring board.
[12] A sheet-like laminate material comprising the resin composition for an insulating layer according to any one of the above [1] to [11].
[13] A multilayer printed wiring board comprising an insulating layer formed by heat curing the resin composition for an insulating layer according to any one of the above [1] to [11] or the sheet-like laminate material according to the above [12] .
[14] A semiconductor device comprising the multilayer printed wiring board according to the above [13].

  According to the present invention, the insulating layer obtained is excellent in low thermal expansion, low dielectric loss tangent and smear removability resin composition for insulating layer, sheet-like laminate material using the resin composition for insulating layer, multilayer printed wiring A plate and a semiconductor device can be provided.

  Hereinafter, although one embodiment of the present invention is explained in full detail, the present invention is not limited to the following embodiments.

[Resin composition for insulating layer]
The resin composition for an insulating layer of the present invention (hereinafter also simply referred to as “resin composition”) comprises (A) a compound having a polybutadiene skeleton (hereinafter also referred to as “(A) component”), (B) an epoxy resin ( Hereinafter, it is also referred to as "(B) component", (C) active ester curing agent (hereinafter referred to as "(C) component") and (D) inorganic filler (hereinafter referred to as "(D) component") The resin composition for an insulating layer, wherein the content of the (D) inorganic filler is 50 to 85 parts by mass with respect to 100 parts by mass on a solid basis of the insulating layer resin composition. .
In addition, in this specification, "solid content conversion" means making only the non volatile matter except volatile components, such as an organic solvent, into a standard. That is, 100 parts by mass in terms of solid content means equivalent to 100 parts by mass of nonvolatile matter.
Hereinafter, each component which the resin composition of this invention contains is demonstrated.

<(A) Compound Having Polybutadiene Skeleton>
The resin composition of the present invention is obtained by using the (A) active ester curing agent, and (D) the low thermal expansibility obtained by highly filling the inorganic filler, and (C) the active ester curing agent. It is possible to improve the smear removability after the laser processing while keeping the low dielectric loss tangent well.
(A) A component may be used individually by 1 type and may use 2 or more types together.

The polybutadiene skeleton possessed by the component (A) is a polymer skeleton having a structural unit derived from 1,3-polybutadiene.
As a structural unit derived from 1,3-polybutadiene, a structural unit having a trans-1,4-bond represented by the following formula (A-1) (hereinafter, also referred to as “structural unit (A-1)”), Structural unit having a cis-1,4-bond represented by the following formula (A-2) (hereinafter, also referred to as “structural unit (A-2)”), 1 represented by the following formula (A-3) , 2-bonded structural units (hereinafter also referred to as “structural units (A-3)”) and the like. In addition, those having a structural unit represented by the following formula (A-4) obtained by hydrogenating the structural unit (A-3) (hereinafter, also referred to as “structural unit (A-4)”) are: It may be mentioned as a polybutadiene skeleton which the component has.

  The polybutadiene skeleton of component (A) is one selected from the group consisting of structural unit (A-1), structural unit (A-2), structural unit (A-3) and structural unit (A-4) It may consist only of the above structural units, or may contain one or more other structural units. As other structural units, styrenes such as styrene and methyl styrene; acrylonitrile; acrylic acid and methacrylic acid; acrylic acid alkyl ester having 1 to 18 carbon atoms, methacrylic acid alkyl ester having 1 to 18 carbon atoms; ethylene and propylene And olefins such as butadiene; and monomers having unsaturated bonds such as vinyl ethers such as vinyl methyl ether. Among these, it is preferable to contain the structural unit derived from the acrylonitrile represented by a following formula (A-5).

  Examples of the component (A) containing a structural unit derived from acrylonitrile include a compound having an acrylonitrile butadiene skeleton obtained by copolymerizing acrylonitrile and butadiene. As an acrylonitrile butadiene frame, what is represented by the following general formula (A-6) is mentioned, for example.

(Wherein x, y and z each independently represent an integer of 1 or more, and each structural unit whose number of structural units is indicated by x, y or z may be linked in any order of arrangement. Preferably, each structural unit may be bound in a block or may be randomly bound.)

  The component (A) may have an epoxidized polybutadiene skeleton. Examples of the epoxidized butadiene skeleton include those represented by the following general formula (A-7).

(In the formula, p, q, r and s each independently represent an integer of 1 or more. In addition, each structural unit whose number of structural units is indicated by p, q, r or s is bonded in any arrangement order. And each structural unit may be bonded in a block shape or in a random shape.)

From the viewpoint of improving smear removability, it is preferable that the component (A) has a reactive group in the molecule while keeping low thermal expansion and low dielectric loss tangent well. In addition, a reactive group means the group which has reactivity with one of the components which the resin composition of this invention contains, and it is preferable that it is a group which has reactivity with an epoxy group.
As said reactive group, 1 or more types chosen from the group which consists of an epoxy group, a hydroxyl group, a carboxy group, an amino group, an amide group, an isocyanato group, an acryl group, a methacryl group, and a vinyl group is mentioned. Among these, an epoxy group and a hydroxyl group are preferable, and an epoxy group is more preferable. That is, the component (A) is preferably a compound having a polybutadiene skeleton and an epoxy group.
When the component (A) has an epoxy group, the epoxy equivalent of the component (A) is preferably 100 to 700 g / eq, more preferably 130 to 600 g / eq, and more preferably 150 to 500 g / eq from the viewpoint of smear removability. More preferable.

The structure of the terminal group of the component (A) is not particularly limited, and examples thereof include one or more selected from the group consisting of the above reactive groups, a hydrogen atom, a methyl group, a vinyl group and the like. Among these, a hydrogen atom, a hydroxyl group and an epoxy group are preferable.
The two terminal groups of component (A) may be the same or different from each other, but are preferably the same.
Examples of the component (A) having an epoxy group at both ends include a compound obtained by reacting an acrylonitrile butadiene copolymer having a carboxy group at the molecular end with an epoxy resin.

The weight-average molecular weight of the component (A) is a weight whose volatilization is suppressed under these conditions from the viewpoint of making the film thickness retention property at the time of heat curing better and the occurrence of plating blistering at the time of heat resistance test. It is preferably an average molecular weight. Although the weight average molecular weight of (A) component is not specifically limited, From said viewpoint, it is 400-20,000, for example.
The weight average molecular weight is measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a standard polystyrene calibration curve.

  The content of the component (A) in the resin composition of the present invention is 100 parts by mass in terms of solid content of the resin composition, from the viewpoint of improving smear removability while keeping low thermal expansion and low dielectric loss tangent favorably. Is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 1.5 parts by mass or more. In addition, from the viewpoint of reducing the surface roughness to improve the fine wiring property, the content of the component (A) is preferably 5 parts by mass or less with respect to 100 parts by mass in terms of solid content of the resin composition, The mass part or less is more preferable, and the 2.7 mass part or less is more preferable.

  In addition, the content of the component (A) based on the resin component in the resin composition for the insulating layer is 2 to 20 based on 100 parts by mass of the resin component in the resin composition from the same viewpoint as above. A mass part is preferable, 3-17 mass parts is more preferable, and 5-15 mass parts is still more preferable.

<(B) Epoxy resin>
Preferred examples of the epoxy resin (B) include epoxy resins having two or more epoxy groups in one molecule.
(B) An epoxy resin may be used individually by 1 type, and may use 2 or more types together.
(B) Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin and the like; phenol novolac type epoxy resin, cresol novolak type Epoxy resins, novolak type epoxy resins such as biphenyl aralkyl novolak type epoxy resins; epoxy resins containing a naphthalene skeleton such as naphthol type epoxy resins, naphthalene type epoxy resins, naphthylene ether type epoxy resins; glycidylamine type epoxy resins, tert- Butyl-catechol type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin Resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, halogenated epoxy resins, and glycidyl ester type epoxy resin.
Among these, from the viewpoint of increasing heat resistance, insulation reliability and peel strength, naphthalene type epoxy resins, biphenyl type epoxy resins, naphthol type epoxy resins and bixylenol type epoxy resins are preferable, and biphenyl aralkyl novolak type epoxy resins are more preferable. . Examples of the biphenyl aralkyl novolak type epoxy resin include compounds having a structural unit represented by the following general formula (B-1), and are preferably compounds represented by the following general formula (B-2).

(Wherein, R ¹ represents a hydrogen atom or a methyl group)

(In the formula, R ¹ is the same as the above, and m is an integer of 1 to 20. A plurality of R ^{1 's} may be the same as or different from each other)

In addition, when a solid epoxy resin is used as the epoxy resin (B), it can be used in combination with a liquid epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin from the viewpoint of the handleability of the resulting resin film. preferable. In that case, the content ratio (solid epoxy resin / liquid epoxy resin) (mass ratio) is preferably 0.5 to 5, from the viewpoints of handleability, electrical properties, and heat resistance of the obtained resin film, preferably 0.8 to 3 is more preferable, and 1 to 2 is more preferable. In addition, as said solid epoxy resin, a biphenyl aralkyl novolak-type epoxy resin is preferable, and as a liquid epoxy resin, bisphenol-A epoxy resin is preferable.
In the present specification, “solid” and “liquid” mean a state at room temperature (25 ° C.).

(B) The epoxy equivalent of the epoxy resin is preferably 150 to 500 g / eq, more preferably 150 to 400 g / eq, and still more preferably 180 to 300 g / eq, from the viewpoints of curability and physical properties of the cured product.
Here, epoxy equivalent is mass (g / eq) of resin per epoxy group, and can be measured based on JISK 7236: 2009.

  A commercial item may be used as the epoxy resin (B). As the commercially available (B) epoxy resin, “Epicoat 828EL” and “YL980” manufactured by Mitsubishi Chemical Co., Ltd., which are bisphenol A type epoxy resins; “jER806H” manufactured by Mitsubishi Chemical Co., Ltd., which is a bisphenol F type epoxy resin; “YL983U”; “HP4032”, “HP4032D”, “HP4032SS” and “EXA4032SS” manufactured by DIC Corporation, which are naphthalene-type bifunctional epoxy resins; “HP4700” manufactured by DIC Corporation, which is a naphthalene-type tetrafunctional epoxy resin; “HP 4710”; “ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd., which is a naphthol type epoxy resin; “NC-3000-H” manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin having a biphenyl structure; 3000-L "and" NC-3 “00”, “YX4000”, “YX4000H”, “YX4000HK” and “YL6121” manufactured by Mitsubishi Chemical Corporation; “YX8800” manufactured by Mitsubishi Chemical Corporation which is an anthracene type epoxy resin; DIC which is a naphthylene ether type epoxy resin “EXA-7310”, “EXA-7311”, “EXA-7311L” and “EXA7311-G3” manufactured by Co., Ltd .; “EX711” and “EX721” manufactured by Nagase ChemteX Corporation, which is a glycidyl ester type epoxy resin, And "R540" manufactured by PRINTEC CO., LTD.

  The content of the epoxy resin (B) in the resin composition of the present invention is 100% by mass conversion to solid content of the resin composition from the viewpoint of improving smear removability while keeping low thermal expansion and low dielectric loss tangent well. 1-30 mass parts is preferable with respect to a part, 3-20 mass parts is more preferable, 5-15 mass parts is still more preferable.

<(C) Active ester curing agent>
The (C) active ester curing agent functions as a curing agent for the (B) epoxy resin. By using the (C) active ester curing agent as a curing agent, the resin composition of the present invention can further reduce the surface roughness and reduce the dielectric loss tangent.
As the (C) active ester curing agent, one type may be used alone, or two or more types may be used in combination.

  (C) As an active ester curing agent, it has an ester group with high reactivity such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester compound of heterocyclic hydroxy group, etc., and (B) epoxy resin The compound etc. which have the hardening effect of can be used.

(C) The active ester curing agent is preferably a compound having two or more active ester groups in one molecule, and in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group. An aromatic compound having two or more active ester groups 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. An aromatic compound having two or more ester groups in the molecule of the aromatic compound is more preferable. The (C) active ester curing agent may contain a linear or multi-branched 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 (B) epoxy resin and the like can be enhanced, and a compound having an aromatic ring If it is, heat resistance can be made high. In particular, from the viewpoint of heat resistance and the like, the (C) 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 the carboxylic acid compound 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.

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 And dicyclopentadienyl diphenol, phenol novolac and the like. Among these, from the viewpoint of heat resistance and solubility, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolak are preferable, and dicyclopentadienyl diphenol is more preferable.
Examples of the thiol compound include benzene dithiol, triazine dithiol and the like.

As the active ester curing agent (C), an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available product may be used.
Commercially available (C) active ester curing agents include those containing a dicyclopentadienyl diphenol structure, acetylated phenol novolacs, benzoylated phenol novolacs, and among these, dicyclopentadienyl. Those containing a diphenol structure are preferred. Specifically, “EXB9451”, “EXB9460”, “EXB9460S-65T”, “HPC-8000-65T” (above, manufactured by DIC Corporation, trade name, activity) as those containing a dicyclopentadienyl diphenol structure. Group equivalent of about 223 g / eq), acetylated product of phenol novolak “DC808” (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent of about 149 g / eq), and benzoylated product of phenol novolac “YLH1026” (manufactured by Mitsubishi Chemical Corporation, active) Group equivalent weight about 200 g / eq) etc. are mentioned.

  (C) 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.

  The content of the (C) active ester curing agent in the resin composition of the present invention is equivalent to the solid content of the resin composition from the viewpoint of maintaining good curability and other cured product physical properties while reducing the dielectric loss tangent. 1-30 mass parts is preferable with respect to 100 mass parts, 3-20 mass parts is more preferable, 5-15 mass parts is still more preferable.

<(D) Inorganic filler>
The resin composition of the present invention is 50 to 85 parts by mass of (D) with respect to 100 parts by mass in terms of solid content of the resin composition, from the viewpoint of achieving both high low thermal expansion, low dielectric loss tangent and smear removability. Contains inorganic filler. From the same viewpoint, the content of the (D) inorganic filler is preferably 55 to 83 parts by mass, more preferably 60 to 82 parts by mass, with respect to 100 parts by mass in terms of solid content of the resin composition. More preferred are parts by weight, particularly 70-80 parts by weight.
(D) An inorganic filler may be used individually by 1 type, and may use 2 or more types together.

(D) As inorganic fillers, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate And strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among these, silica is preferred. Examples of the silica include amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, mesoporous silica and the like, and among these, fused silica is more preferable. As fused silica, spherical fused silica is preferable.
A commercial item may be used as the inorganic filler (D). Examples of commercially available (D) inorganic fillers include “SOC2” and “SOC1” manufactured by Admatex Co., Ltd., which are fused spherical silica.

(D) The average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 3 μm or less, further preferably 1 μm or less, and particularly preferably 0.7 μm or less from the viewpoint of fine wiring formability. On the other hand, from the viewpoint of suppressing an increase in viscosity when the resin composition is used as a varnish and obtaining good handleability, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more.
(D) The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on the Mie scattering theory. Specifically, it can be measured by preparing a particle size distribution of (D) inorganic filler on a volume basis with a laser diffraction / scattering particle size distribution measuring apparatus and setting the median diameter as the average particle diameter. As the measurement sample, those obtained by dispersing (D) an inorganic filler in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-950” manufactured by Horiba, Ltd. or the like can be used.

From the viewpoint of improving the moisture resistance of the cured product (D) and the dispersibility of the (D) inorganic filler, the (D) inorganic filler is preferably surface-treated.
(D) As a surface treatment agent for inorganic fillers, epoxy silane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. A silane coupling agent is mentioned. Among these, from the viewpoint of storage stability and adhesiveness, aminosilane coupling agents are preferable.
The aminosilane coupling agent is a silane coupling agent having an amino group, and specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N- Phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane, N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane and the like.
The surface treatment agent may be used alone or in combination of two or more.

<(E) phenoxy resin>
The resin composition of the present invention preferably contains (E) a phenoxy resin. (E) By containing the phenoxy resin, the adhesion between the insulating layer and the conductor layer tends to be improved, and the roughened shape of the surface of the insulating layer tends to be small and dense.
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. It refers 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 (E) phenoxy resin, and the weight is Those having an average molecular weight of less than 10,000 are classified as (B) epoxy resin.
The weight average molecular weight of the (E) phenoxy resin 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 insulating layer. (E) When the weight average molecular weight of the phenoxy resin is within the above range, the generation of blisters in the conductor layer tends to be suppressed.
As the (E) phenoxy resin, one type may be used alone, or two or more types may be used in combination.

  (E) 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 kinds of skeletons selected from naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, trimethylcyclohexane skeleton and copolymer skeleton of styrene and glycidyl methacrylate are mentioned. Among these, a phenoxy resin having a biphenyl skeleton is preferable from the viewpoint of improving the chemical resistance of the insulating layer and from the viewpoint of facilitating provision of appropriate unevenness to the insulating layer by the oxidizing agent. The terminal of the phenoxy resin (E) may be any functional group such as phenolic hydroxyl group and epoxy group.

  (E) The phenoxy resin is, for example, a bisphenol compound containing a trimethylcyclohexane structure or a bisphenol compound containing a terpene structure and a bifunctional epoxy resin as raw materials. It can be manufactured by reacting in an equivalent ratio of about 1: 0.9 to 1: 1.1.

  When the resin composition of the present invention contains (E) a phenoxy resin, the content thereof is 100% in terms of solid content of the resin composition from the viewpoint of obtaining handleability, adhesiveness with a conductor layer and appropriate roughness. 0.5-20 mass parts is preferable with respect to a part, 0.7-10 mass parts is more preferable, 0.7-2 mass parts is still more preferable.

<(F) Hardening accelerator)>
The resin composition of the present invention preferably further comprises (F) a curing accelerator.
(F) As a hardening accelerator, what is necessary is just to be able to accelerate | stimulate the bridge | crosslinking and hardening of (B) component and (C) component, and an amine type hardening accelerator, a guanidine type hardening accelerator, and an imidazole type hardening accelerator. Agents, phosphonium-based curing accelerators, metal-based curing accelerators, and the like. Among these, amine curing accelerators are preferable from the viewpoint of the curability of the resin composition and the physical properties of the cured product.
Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5, 4,0] -undecene etc. are mentioned.
(F) A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
When the resin composition of this invention contains (F) hardening accelerator, the content is 100 mass parts of conversion of solid content of a resin composition from a viewpoint of sclerosis | hardenability and hardened | cured material property of a resin composition. 0.005 to 3 parts by mass is preferable, and 0.01 to 1 part by mass is more preferable.

<Other ingredients>
The resin composition of the present invention may contain components (hereinafter also referred to as “other components”) other than the above-described components, as long as the object of the present invention is not impaired. As other components, thermoplastic resins other than the component (E) (hereinafter, also referred to as "other thermoplastic resins"), thermosetting resins other than the components (B) and (C) (hereinafter, "others" Also referred to as a thermosetting resin), an organic filler, a polymerization initiator, an organic solvent, other additives, and the like. One of these may be used alone, or two or more may be used in combination.

(Other thermoplastic resins)
As other thermoplastic resins, phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide imide resin, polyether sulfone resin, cycloolefin polymer, polysulfone resin and the like can be mentioned.
When the resin composition of the present invention contains another thermoplastic resin, the content thereof is preferably 0.01 to 5 parts by mass, and 0.5 to 0.5 parts by mass with respect to 100 parts by mass on a solid basis of the resin composition. 3 parts by mass is more preferred. The resin composition of the present invention may not contain any other thermoplastic resin, depending on the desired performance.

(Other thermosetting resins)
Other thermosetting resins include vinyl benzyl resin, acrylic resin, maleimide resin, blocked isocyanate resin and the like. The resin composition of the present invention may not contain any other thermosetting resin, depending on the desired performance.

(Organic filler)
Examples of the organic filler include silicon powder, nylon powder, fluorine powder, rubber particles and the like.
When the resin composition of the present invention contains an organic filler, the content thereof is preferably 0.01 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition. Part is more preferred. The resin composition of the present invention may not contain an organic filler, depending on the desired performance.

(Polymerization initiator)
Examples of the polymerization initiator include dialkyl peroxide-based organic peroxides and the like.
When the resin composition of the present invention contains a polymerization initiator, the content thereof is preferably 0.005 to 2 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass in terms of solid content of the resin composition. Part is more preferred. The resin composition of the present invention may not contain a polymerization initiator depending on the desired performance.

(Other additives)
Other additives include flame retardants such as inorganic flame retardants and resin flame retardants; thickeners such as olben and benton; adhesion imparting agents such as imidazole, thiazole and triazole; colorants; antifoaming agents and the like Can be mentioned. The resin composition of the present invention may not contain the above-mentioned other additives, depending on the desired performance.

(Organic solvent)
The resin composition of the present invention may be a varnish-like resin composition containing an organic solvent (hereinafter also referred to as "resin varnish") from the viewpoint of handleability.
Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”), methyl isobutyl ketone, and cyclohexanone; acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Examples include ester solvents; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; 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.

Physical properties of cured product of resin composition for insulating layer
The preferable cured product physical properties of the resin composition for an insulating layer of the present invention are as follows.

  The linear thermal expansion coefficient of the cured product of the resin composition of the present invention is preferably 30 ppm / ° C. or less, more preferably 25 ppm / ° C. or less, still more preferably 23 ppm / ° C. or less, particularly preferably 20 ppm / ° C. or less. While being able to suppress generation | occurrence | production of curvature as the linear thermal expansion coefficient is the said range, distortion of an insulating layer and a conductor layer is prevented, and a highly reliable multilayer printed wiring board can be obtained. Although there is no restriction | limiting in particular in the lower limit of a linear thermal expansion coefficient, For example, it is 4 ppm / degrees C or more. In addition, a linear thermal expansion coefficient can be measured by the method as described in an Example. The cured product of the resin composition is obtained by heating the resin composition at 200 ° C. for 90 minutes.

  0.0054 or less is preferable, as for the dielectric loss tangent of the hardened | cured material of the resin composition of this invention, 0.0052 or less is more preferable, 0.0050 or less is still more preferable, 0.0047 or less is especially preferable. When the dielectric loss tangent is in the above range, it is possible to suppress the loss of loss due to the increase in frequency. The lower limit value of the dielectric loss tangent is not particularly limited, but may be, for example, 0.0010 or more, or 0.0020 or more. The dielectric loss tangent can be measured by the method described in the examples. The cured product of the resin composition is obtained by heating the resin composition at 200 ° C. for 90 minutes.

  The arithmetic average roughness (Ra) of the surface of the insulating layer after roughening treatment formed from the resin composition of the present invention is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 100 nm or less 60 nm or less is particularly preferable. When the arithmetic average roughness (Ra) is within the above range, excellent fine wiring properties can be obtained. The lower limit value of the arithmetic average roughness (Ra) may be, for example, 10 nm or more or 20 nm or more from the viewpoint of adhesion to the conductor layer. The surface roughness can be measured according to JIS B0601: 1994.

<Method of producing resin composition for insulating layer>
The resin composition of the present invention is blended with the above components and kneaded by means of kneading means such as a triple roll, ball mill, bead mill, sand mill or the like; if necessary, stirring means such as a high-speed rotary mixer, super mixer, planetary mixer, etc. Can be manufactured by mixing, etc.

<Use of resin composition>
The resin composition of the present invention is suitable as a resin composition for forming an insulating layer (resin composition for insulating layer of multilayer printed wiring board) in the production of a multilayer printed wiring board, and a conductor layer is formed by plating. Resin composition (resin composition for insulating layer of multilayer printed wiring board in which conductor layer is formed by plating), and resin composition for forming buildup layer (build of multilayer printed wiring board) It is further suitable as a resin composition for up layers.
The resin composition of the present invention may be applied to a circuit board in the state of a resin varnish to form an insulating layer, but industrially, it may be used in the form of a sheet-like laminate material such as a resin film or a prepreg. preferable. The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.

[Sheet laminated material]
The sheet-like laminate material of the present invention contains the resin composition for an insulating layer of the present invention.
The sheet-like laminate material of the present invention includes a resin film with a support having a resin composition layer formed by layering the resin composition of the present invention on a support, and the resin composition of the present invention as a sheet-shaped reinforcing substrate. And the like, such as a prepreg formed by Hereinafter, the suitable aspect of a sheet-like laminated material is demonstrated.

<Resin film with support>
The resin film with a support can be produced, for example, by applying the above-mentioned resin varnish on a support with a die coater or the like and then drying the organic solvent by a method such as heating or hot air blowing.
The drying conditions are preferably conditions in which the content of the organic solvent in the resin composition layer after drying is 10% by mass or less, and more preferably conditions in which the content is 5% by mass or less. Specific conditions vary depending on the amount of organic solvent in the resin varnish, boiling point, etc., for example, drying a resin varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for 3 to 10 minutes. Thus, the resin composition layer can be formed.
The thickness of the resin composition layer is preferably 1 to 150 μm, more preferably 2 to 100 μm, still more preferably 3 to 70 μm, and particularly preferably 5 to 50 μm, from the viewpoint of achieving both insulation and thinning of the printed wiring board. preferable.
The resin film with a support may have a plurality of resin composition layers. Moreover, you may have a protective film in the surface on the opposite side to the support body of a resin composition layer from a viewpoint of preventing adhesion and damage | wound etc. to the surface of a resin composition layer.

Examples of the support include organic resin films, metal foils, release papers and the like.
Examples of the material for the organic resin film include polyolefin such as polyethylene and polyvinyl chloride; polyester such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; polycarbonate and polyimide. Among these, PET is preferable in terms of cost and handling.
As metal foil, copper foil, aluminum foil, etc. are mentioned. When a copper foil is used 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, an electrolytic copper foil, or the like can be used as the copper foil. The thickness of the copper foil is, for example, 2 to 36 μm. When using thin copper foil, you may use copper foil with a carrier from a viewpoint of improving workability | operativity.
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, and more preferably 25 to 45 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 150 μm or less from the viewpoint of energy saving and the like.

  As a protective film, the film which has the material similar to the said support body is mentioned. The thickness of the protective film is, for example, 1 to 40 μm. The resin film with a support on which the protective film is laminated can also be wound and stored in a roll.

Prepreg
The prepreg of the present invention is obtained by impregnating the resin composition of the present invention into a sheet-like reinforcing substrate.
The prepreg of the present invention can be produced by, for example, impregnating the resin composition of the present invention into a sheet-like reinforcing base made of fibers by a hot melt method or a solvent method, and heating and semi-curing. The hot melt method is a method of producing a prepreg by laminating or directly coating a resin composition on a sheet-like reinforcing substrate without dissolving it in an organic solvent. The solvent method is a method in which a sheet-like reinforcing base material is immersed in a resin varnish, the resin varnish is impregnated in the sheet-like reinforcing base material, and then dried.

A well-known thing used for the laminated board for various electric insulating materials can be used as a sheet-like reinforcement base material. Materials of the sheet-like reinforcing substrate include: natural fibers such as paper and cotton linter; inorganic fibers such as glass fiber; organic fibers such as aramid, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene, acrylic and the like; Can be mentioned. Among these, glass fiber is preferable from the viewpoint of flame retardancy. Glass fiber substrates include woven fabrics using E glass, C glass, D glass, S glass, etc. or woven glass fibers obtained by bonding short fibers with an organic binder; glass fibers mixed with cellulose fibers, etc. Can be mentioned.
These sheet-like reinforcing substrates have, for example, shapes such as woven fabric, non-woven fabric, rovinck, chopped strand mat, surfacing mat and the like. In addition, a material and a shape are selected by the use and performance of the target molded object, 1 type may be used independently, and 2 or more types of materials and shapes can also be combined as needed.
The thickness of the sheet-like reinforcing substrate can be, for example, about 0.01 to 0.5 mm, which is surface-treated with a silane coupling agent or the like, or mechanically opened. It is preferable from the viewpoints of heat resistance, moisture resistance and processability.
One prepreg may be used, and if necessary, for example, 2 to 20 sheets may be overlapped and used.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present invention comprises the insulating layer resin composition of the present invention or the insulating layer formed by heat curing the sheet-like laminate material of the present invention.
Hereinafter, an example of a method of manufacturing a multilayer printed wiring board using the resin film with a support of the present invention will be described.

<Manufacturing method of multilayer printed wiring board using resin film with support>
The multilayer printed wiring board of this invention can be manufactured by laminating | stacking the resin film with a support body of this invention on a circuit board, for example. Specifically, for example, it can be produced by a production method including the following steps (1) to (6).
(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 laminating step (1)].
(2) A step of thermally curing the laminated resin film to form an insulating layer [hereinafter referred to as an 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) A step of roughening the surface of the insulating layer [hereinafter referred to as a 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)].
In addition, you may peel or remove the support body which a resin film with a support body has after process (1), (2) or (3).

The laminating step (1) is a step of laminating the resin film of the present invention on one side or both sides of the circuit board.
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 that by which the conductor layer (circuit) by which pattern processing was carried out was carried out on the single side | surface or both surfaces of the above board | substrates here. 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. Included in the circuit board. The surface of the conductor layer may be previously roughened by blackening treatment, copper etching, or the like.

  In the above laminate, when the resin film has a protective film, after removing the protective film, the resin film and the circuit board are preheated if necessary, and the resin film is pressed and heated to the circuit board. Crimp. In the resin film of the present invention, a method of laminating on a circuit board under reduced pressure by vacuum lamination is suitably used. The lamination conditions are, for example, a pressure reduction of about 20 mmHg (26.7 hPa) or less for about 10 to 120 seconds, and then the pressure bonding temperature (lamination temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (lamination pressure) is preferably 0 It is preferable to laminate at a pressure of 1 to 1.5 MPa, more preferably 0.5 to 1.2 MPa, and a pressure bonding time (lamination time) of preferably 5 to 180 seconds. 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. Then, after cooling to room temperature (25 degreeC) vicinity, when peeling a support body, you may peel.

The insulating layer forming step (2) is a step of thermosetting the resin film laminated on the circuit board to form an insulating layer.
Although the conditions of thermosetting may be suitably selected according to the kind of resin component in resin composition, content, etc., 150-220 degreeC is preferable and 160-210 degreeC of a heating temperature is more preferable. Moreover, 20 to 180 minutes are preferable and, as for a heat time, 30 to 120 minutes are more preferable. The heat curing may be performed in one step or in two steps.
After heat curing, in the case of peeling off the support, it may be peeled off.

After forming the insulating layer, via holes (3), via holes, through holes and the like are formed.
Drilling can be performed, for example, by a method such as drilling, laser, plasma, or a combination thereof, but it is preferable to use a laser such as a carbon dioxide gas laser or a YAG laser.
In the case where the support is not peeled off before drilling, it is peeled off before the roughening treatment step (4) after carrying out the drilling step (3).

In the roughening treatment step (4), the surface of the insulating layer is roughened.
In the case of wet plating, the surface of the insulating layer is subjected to a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order to form an uneven anchor.
In the swelling treatment with the swelling solution, for example, the insulating layer is immersed in the swelling solution at 50 to 80 ° C. for 5 to 20 minutes. The swelling solution may, for example, be an alkaline solution or a surfactant solution, preferably an alkaline solution. Examples of the alkaline solution include sodium hydroxide solution and potassium hydroxide solution. Commercially available swelling liquids include Swelling Dip Securiganth (registered trademark) P (Swelling Dip Securiganth P), Swelling Dip Securiganth (registered trademark) SBU (Swelling Dip Securiganth P) manufactured by Atotech Japan Co., Ltd. SBU).
In the roughening treatment with an oxidizing agent, for example, the insulating layer is immersed in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes. Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate, sodium permanganate and the like are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. The permanganate concentration in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP, Dosing Solution Securigans (registered trademark) P manufactured by Atotech Japan Co., Ltd.
In the neutralization treatment with the neutralization liquid, for example, the insulating layer is immersed in the neutralization liquid at 30 to 50 ° C. for 3 to 10 minutes. An acidic aqueous solution is preferable as the neutralization solution. As a neutralization solution marketed, reduction solution thin security G (trademark) P by Atotech Japan KK etc. are mentioned.
After the roughening treatment, the insulating layer may be dried, for example, at 50 to 120 ° C. for 10 to 60 minutes, preferably at 60 to 100 ° C. for 20 to 40 minutes.
The above wet roughening treatment step (4) can also be said to be a desmear step of removing the smear generated in the drilling step (3).
Although the wet roughening treatment method has been described above, the insulating layer surface may be dry roughened using plasma treatment or the like.
Moreover, the suitable arithmetic mean roughness (Ra) of the insulating layer surface after a roughening process is as above-mentioned.

In the conductor layer forming step (5), a conductor layer is formed on the surface of the roughened insulating layer by plating.
Examples of the plating method include dry plating, wet plating and the like.
Examples of dry plating include known methods such as vapor deposition, sputtering, and ion plating.
Although wet plating is preferably performed by combining electroless plating and electrolytic plating, a plating resist having a pattern reverse to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating.
Examples of the metal for plating include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, and chromium. Among these, copper is preferable.

  Thereafter, in the circuit formation step (6), the conductor layer is patterned. As a method of forming a circuit, a known method such as a subtractive method, a full additive method, a semi-additive method (SAP), or a modified semi-additive process (m-SAP) can be used. .

<Multilayer printed wiring board using a prepreg>
Next, an example of a method for producing a multilayer printed wiring board using the prepreg of the present invention will be described. First, one or several sheets of the prepreg of the present invention are stacked on the above circuit board, held by a metal plate via a release film, and vacuum pressed and laminated under pressure and heating conditions. The pressurization ^{condition, 5~40kgf / cm 2 (49 ×} 10 4 ~392 × 10 4 N / m 2) is preferred, the heating condition is preferably 20 to 100 minutes at 120 to 200 [° C.. Moreover, it is also possible to heat-harden after laminating a prepreg on a circuit board by a vacuum laminating method. Thereafter, the hardened prepreg surface is roughened in the same manner as the above method, and then a conductor layer can be formed by plating to produce a multilayer printed wiring board.

[Semiconductor device]
The semiconductor device of the present invention includes the multilayer printed wiring board of the present invention.
The semiconductor device of the present invention can be manufactured, for example, by mounting a semiconductor chip on 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 in the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, the wire bonding mounting method, flip chip mounting method, no bump A mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF), and the like can be given.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The resin composition for insulating layers obtained in each example was evaluated by the following method.

[Smear removability]
In evaluating the smear removability, an evaluation substrate was prepared according to the following procedures (1) to (5).

(1) Base treatment of inner layer circuit board Glass cloth base epoxy resin double-sided copper clad laminate with inner layer circuit (copper foil thickness 18 μm, substrate thickness 0.3 mm, manufactured by Hitachi Chemical Co., Ltd .: MCL-E- The copper surface was subjected to a roughening treatment by etching 1 μm of both surfaces of 679 FG) using “CZ 8100” manufactured by MEC CO., LTD. To obtain a roughened inner layer circuit board.
(2) Lamination of Resin Film with Support Using the batch-type vacuum press laminator (trade name: MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), the above-mentioned (1 The resin composition layer was laminated on both sides of the inner layer circuit board obtained in 2.) in a state of facing the inner layer circuit board. The lamination was performed for 30 seconds under a reduced pressure of 13 hPa or less for 30 seconds, and then performed for 30 seconds under the conditions of a pressure bonding temperature of 100 ° C. and a pressure bonding pressure of 0.5 MPa.
(3) Curing of Resin Composition The laminated resin film was heated at 130 ° C. for 30 minutes and then heated at 170 ° C. for 30 minutes to form an insulating layer formed by curing the resin film.
(4) Via hole formation Using a CO ₂ laser processing machine (trade name: LC-2E21B / 1C, manufactured by Hitachi Via Mechanics Co., Ltd.), mask diameter 1.60 mm, focus offset value 0.050, pulse width 18 μs, power 0 The insulating layer was drilled under the conditions of 66 W, aperture 2, shot number 5, and burst mode to form a via hole having a top diameter (diameter) of 50 μm on the surface of the insulating layer. Thereafter, the support was peeled off.
(5) Desmear treatment The inner layer circuit board on which the insulating layer is formed is swelled in “Swelling Dip Securigant P” (glycol ether, sodium hydroxide aqueous solution, manufactured by Atotech Japan Co., Ltd.) at 60 ° C. Immerse in water for 15 minutes, and then as a roughening solution, soak in “Concentrate Compact P” (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution, manufactured by Atotech Japan Co., Ltd.) at 80 ° C. for 20 minutes. As a neutralizing solution, an evaluation substrate was prepared by immersing in “Reduction Sholycine Securigant P” (an aqueous solution of sulfuric acid, manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes and then drying at 80 ° C. for 10 minutes. .

The periphery of the via hole bottom of the evaluation substrate obtained above was observed with a scanning electron microscope (SEM), the maximum smear length from the wall surface of the via hole bottom was measured from the image, and the bottom of the via hole was measured based on the following evaluation criteria. Smear removability was evaluated.
(Evaluation criteria)
A: Maximum smear length is less than 3 μm B: Maximum smear length is 3 μm or more and less than 5 μm C: Maximum smear length is 5 μm or more

[Arithmetic mean roughness (Ra)]
About the evaluation board, using a non-contact type surface roughness meter (Bee Coins Instruments Co., Ltd., trade name: WYKONT 3300), three locations arbitrarily selected under the conditions of VSI contact mode, 50 × lens, measurement range 121 μm × 92 μm Was measured, and the average value thereof was evaluated as arithmetic average roughness (Ra) based on the following evaluation criteria.
(Evaluation criteria)
A: Arithmetic mean roughness (Ra) was 60 nm or less.
B: Arithmetic mean roughness (Ra) was over 60 nm.

[Linear thermal expansion coefficient]
The resin film with a support obtained in each Example was heated at 200 ° C. for 90 minutes for heat curing, and then the support was peeled off to obtain a sheet-like cured product. Next, this sheet-like cured product was cut into a length of about 15 mm and a width of about 5 mm to obtain a test piece for thermomechanical analysis. The thermomechanical analysis is performed by a tensile load method using a thermomechanical analyzer (trade name: Thermo Plus TMA8310, manufactured by Rigaku Corporation). After mounting the above test piece on the apparatus, the load is 1 g and the heating rate is 5 ° C. The measurement was continuously performed twice under the measurement conditions of 1 / min, the average linear thermal expansion coefficient (ppm / ° C) from 0 ° C to 50 ° C in the second measurement was calculated, and this was used as the linear thermal expansion coefficient .

[Dielectric loss tangent]
The resin film with a support obtained in each Example was heated at 200 ° C. for 90 minutes for heat curing, and then the support was peeled off to obtain a sheet-like cured product. Next, this sheet-like cured product was cut into a length of 80 mm and a width of 2 mm to obtain a test piece for dielectric loss tangent measurement. With respect to this test piece, dielectric loss tangent was measured by “cavity resonance perturbation method” using “HP8362B” manufactured by Agilent Technologies under the conditions of a measurement frequency of 10 GHz and a measurement temperature of 25 ° C. The measurement was performed on two test pieces, and the average value was taken as the dielectric loss tangent.

Examples 1 to 6, Comparative Example 1
Each component shown in Table 1 is blended in the composition shown in Table 1 (unit: part by mass; however, in the case of a solution or dispersion, the solid content is shown in an equivalent amount), and is uniformly dispersed with a high-speed rotary mixer to obtain a resin. A varnish was prepared.
Next, the resin varnish obtained is coated on a PET film (made by Toray Film Co., Ltd., trade name: SY (01), thickness: 38 μm) which is a support, then dried and attached to a support A resin film was prepared. In addition, the thickness of application is adjusted so that the thickness of the resin composition layer after drying will be 40 micrometers, and, as for drying, the residual solvent in the resin composition layer after drying is 3.0 mass%. went. The evaluation results of the obtained resin film are shown in Table 1.

[(A) Compound having polybutadiene skeleton]
TSR-601: carboxy group-terminated butadiene nitrile rubber (CTBN) modified epoxy resin (manufactured by DIC Corporation, trade name, epoxy equivalent: 450 to 500 g / eq)
-PB 4700: Epoxidized polybutadiene (manufactured by Daicel Chemical Industries, Ltd., trade name, epoxy equivalent: 152 to 178 g / eq)
[(B) Epoxy resin]
840-S: bisphenol A type epoxy resin (manufactured by DIC Corporation, epoxy equivalent: 180 to 190 g / eq)
NC-3000-H: biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name, epoxy equivalent: 288 g / eq)
[(C) Active ester curing agent]
HPC-8000-65T: Active ester curing agent (active ester compound containing dicyclopentadiene type diphenol structure) (manufactured by DIC Corporation, trade name, active group equivalent: 223 g / eq)
[(D) Inorganic filler]
SC2050KNK: spherical fused silica (average particle size 0.5 μm, Admatex Co., Ltd. "SOC2", carbon per unit area) surface-treated with phenylaminosilane based coupling agent ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) Amount 0.39 mg / m ² )
[(E) Phenoxy resin]
YX7200B35: Phenoxy resin containing a skeleton derived from a biphenyl type epoxy resin and a bisphenol compound (1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane) having a trimethylcyclohexane structure (Mitsubishi, Ltd.) Chemical Co., Ltd., Epoxy equivalent: 3,000 to 16,000 g / mol)
[(F) Curing accelerator]
DMAP: 4-dimethylaminopyridine

  As apparent from the results of Table 1, the insulating layer obtained from the resin film with a support according to Examples 1 to 6 has excellent smear removability while maintaining excellent low thermal expansion and low dielectric loss tangent. Have. Moreover, the insulating layer of Example 1 and 2 had low surface roughness Ra, and was excellent also in fine wiring property. On the other hand, the cured product obtained from the resin sheet of Comparative Example 1 in which the component (A) was not used was inferior in smear removability. From these results, it can be seen that the insulating layer obtained from the resin composition for an insulating layer of the present invention is excellent in low thermal expansion, low dielectric loss tangent and smear removability.

  With the resin composition for an insulating layer of the present invention, an insulating layer having excellent smear removability can be obtained while maintaining a good linear thermal expansion coefficient and a dielectric loss tangent even when the inorganic filler is highly filled particularly. . Therefore, the resin composition for an insulating layer of the present invention, a sheet-like laminate material using the resin composition for an insulating layer, a multilayer printed wiring board and a semiconductor device are electric products such as computers, mobile phones, digital cameras, and televisions; It can be widely used as a vehicle such as a motorcycle, a car, a train, a ship, and an aircraft.

Claims (14)

A resin composition for an insulating layer comprising (A) a compound having a polybutadiene skeleton, (B) an epoxy resin, (C) an active ester curing agent, and (D) an inorganic filler,
The resin composition for insulating layers whose content of the said (D) inorganic filler is 50-85 mass parts with respect to solid content conversion 100 mass parts of this resin composition for insulating layers.   The resin composition for insulating layers of Claim 1 whose content of the said (A) component is 0.5-5 mass parts with respect to solid content conversion 100 mass parts of the said resin composition for insulating layers. .   The resin composition for insulating layers according to claim 1 or 2, wherein the component (A) is a compound having a polybutadiene skeleton and an epoxy group.   The insulation according to any one of claims 1 to 3, wherein the content of the component (B) is 1 to 30 parts by mass with respect to 100 parts by mass on a solid basis of the resin composition for the insulating layer. Layer resin composition.   The component (B) is at least one selected from the group consisting of naphthalene type epoxy resins, biphenyl type epoxy resins, naphthol type epoxy resins and bixylenol type epoxy resins. The resin composition for insulating layers as described in 2.   The insulation according to any one of claims 1 to 5, wherein the content of the component (C) is 1 to 30 parts by mass with respect to 100 parts by mass on a solid basis of the resin composition for an insulating layer. Layer resin composition.   The insulation according to any one of claims 1 to 6, wherein the content of the component (D) is 70 to 80 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition for an insulating layer. Layer resin composition.   The resin composition for insulating layers of any one of Claims 1-7 whose said (D) component is a silica.   The resin composition for insulating layers of any one of Claims 1-8 whose said (D) component is surface-treated by the silane coupling agent which has an amino group.   The insulation according to any one of claims 1 to 9, wherein the content of the component (A) is 2 to 20 parts by mass with respect to 100 parts by mass of the resin component in the resin composition for an insulating layer. Layer resin composition.   The resin composition for insulating layers of any one of Claims 1-10 used for the buildup layer of a multilayer printed wiring board.   The sheet-like laminated material containing the resin composition for insulating layers of any one of Claims 1-11.   The multilayer printed wiring board containing the insulating layer formed by thermosetting the resin composition for insulating layers of any one of Claims 1-11, or the sheet-like lamination material of Claim 12.   A semiconductor device comprising the multilayer printed wiring board according to claim 13.