JP6163803B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition. Furthermore, it is related with the sheet-like laminated material, multilayer printed wiring board, and semiconductor device containing the said resin composition.

  2. Description of the Related Art In recent years, electronic devices have been reduced in size and performance, and in multilayer printed wiring boards, build-up layers have been multilayered, and miniaturization and high density of wiring have been demanded.

  Various approaches have been made against this. For example, Patent Document 1 discloses an epoxy containing (a) an epoxy resin, (b) an active ester compound, (c) a triazine structure-containing phenol resin, (d) a maleimide compound, and (e) a phenoxy resin. A resin composition is described, and it is further described that an inorganic filler may be contained for the purpose of lowering the linear expansion coefficient. And the hardened | cured material obtained by hardening | curing this resin composition forms the conductor layer which has high adhesiveness by plating, even when the roughness of the roughening surface which roughened the surface of this hardened | cured material is comparatively small For example, when it is used as an insulating layer of a multilayer printed wiring board, it becomes a material that is extremely advantageous for miniaturization of a conductor layer formed on the insulating layer, and the cured product has a low linear expansion coefficient. Therefore, it is disclosed that cracks due to the difference in linear expansion coefficient between the conductor layer and the insulating layer are hardly generated.

JP 2010-90238 A

  According to the knowledge of the present inventors, a multilayer printed wiring board was produced using a resin composition containing an active ester compound and a large amount of an inorganic filler in order to achieve further low thermal expansion, high adhesion, and low dielectric loss tangent. As a result, it has been found that the peel strength of the cured product of these resin compositions tends to be low, and the resin composition tends to become brittle when it is made into a sheet form.

  Therefore, the problem to be solved by the present invention is to provide a resin composition having a low dielectric loss tangent of a cured product of the resin composition, a high peel strength, and excellent flexibility in a sheet form. And

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent, and (C) an inorganic filler. When the nonvolatile component in the resin composition is 100% by mass, the content of (C) the inorganic filler is 50% by mass or more, and (C) the inorganic filler is 100 parts by mass, A) The resin composition characterized in that the epoxy resin having an ester skeleton is 1 to 20 parts by mass, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent and (C) an inorganic filler, wherein 100% by mass of the non-volatile component in the resin composition When (C) inorganic filler content is 50 mass% or more, and (C) inorganic filler is 100 mass parts, (A) 1-20 mass parts of epoxy resin having an ester skeleton A resin composition characterized by the above.
[2] (A) The resin according to [1], wherein the epoxy resin having an ester skeleton is at least one selected from a glycidyl ester type epoxy resin, a dimer acid-modified epoxy resin, and an alicyclic epoxy resin having an ester skeleton. Composition.
[3] (A) Epoxy resins having an ester skeleton are diglycidyl phthalate epoxy resin, diglycidyl hexahydrophthalate epoxy resin, and 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxy The resin composition according to [1] or [2], which is one or more selected from one or more selected from rates.
[4] (A) The resin composition according to any one of [1] to [3], wherein the epoxy equivalent of the epoxy resin having an ester skeleton is 100 to 1000.
[5] The resin composition according to any one of [1] to [4], wherein the average particle size of the inorganic filler (C) is 0.01 to 5 μm.
[6] (A) A combination of an epoxy resin having an ester skeleton and another epoxy resin, (A) a glycidyl ester type epoxy resin as an epoxy resin having an ester skeleton, and a biphenyl type epoxy resin as another epoxy resin (C) Resin composition in any one of [1]-[5] containing a silica as an inorganic filler.
[7] (A) An epoxy resin having an ester skeleton and another epoxy resin are used in combination, and (A) an epoxy resin having an ester skeleton is a diglycidyl phthalate epoxy resin or a diglycidyl hexahydrophthalate epoxy resin The resin composition according to any one of [1] to [6], including biphenyl type epoxy resin as another epoxy resin, and (C) silica having an average particle diameter of 0.01 to 5 μm as an inorganic filler. .
[8] The resin composition according to any one of [1] to [7], further comprising (D) a curing accelerator.
[9] The resin composition according to any one of [1] to [8], further comprising (E) a polymer resin.
[10] The resin composition according to any one of [1] to [9], which is a resin composition for a buildup layer of a multilayer printed wiring board.
[11] A sheet-like laminate material comprising the resin composition according to any one of [1] to [10].
[12] An adhesive film or prepreg containing the resin composition according to any one of [1] to [10].
[13] A multilayer printed wiring board in which an insulating layer is formed by thermosetting the resin composition according to any one of [1] to [10].
[14] A semiconductor device using the multilayer printed wiring board according to [13].

  By using the resin composition of the present invention, it has become possible to provide a resin composition having a low dielectric loss tangent of a cured product of the resin composition, a high peel strength, and excellent flexibility in a sheet-like form. . Furthermore, according to this invention, the heat resistance of the hardened | cured material of a resin composition can be improved.

  The present invention is a resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent and (C) an inorganic filler, and 100% by mass of the nonvolatile component in the resin composition When (C) inorganic filler content is 50 mass% or more, and (C) inorganic filler is 100 mass parts, (A) 1-20 mass parts of epoxy resin having an ester skeleton It is a resin composition characterized by being. Hereinafter, the compounding components of the resin composition will be described in detail.

<(A) Epoxy resin having ester skeleton>
The epoxy resin having an ester skeleton used in the present invention is not particularly limited, and reacts a compound having a carboxyl group in the molecule with epichlorohydrin or a compound having a carboxyl group in the molecule. It can be obtained by reacting an epoxy resin. In particular, as an epoxy resin having an ester skeleton, an epoxy resin having two or more ester skeletons is preferable from the viewpoint of providing a resin composition having excellent sheet form flexibility.

  As specific examples of the epoxy resin having an ester skeleton, a glycidyl ester type epoxy resin, a dimer acid-modified epoxy resin, and an alicyclic epoxy resin having an ester skeleton are preferable, the glass transition temperature is high, and the heat resistance of the cured product is improved. The glycidyl ester type epoxy resin and the alicyclic epoxy resin having an ester skeleton are more preferable.

  Examples of glycidyl ester type epoxy resins include diglycidyl phthalate type epoxy resins, diglycidyl hexahydrophthalate type epoxy resins, diglycidyl terephthalate type epoxy resins, diglycidyl ester type isophthalate epoxy resins, and various types thereof. Examples include isomers, and from the viewpoint of improving heat resistance, diglycidyl phthalate epoxy resin and diglycidyl hexahydrophthalate epoxy resin are preferred.

  The diglycidyl phthalate type epoxy resin is represented by the following formula (1). Examples of commercially available products include “Epomic R508” (manufactured by Mitsui Chemicals), “EX-721” (manufactured by Nagase ChemteX Corporation), and the like.

  The hexahydrophthalic acid diglycidyl ester type epoxy resin is represented by the following formula (2). Examples of commercially available products include “Epomic R540” (manufactured by Mitsui Chemicals), “AK-601” (manufactured by Nippon Kayaku Co., Ltd.), “EX-722L” (manufactured by Nagase ChemteX Corporation), and the like. .

  Examples of the terephthalic acid diglycidyl ester type epoxy resin include “EX-711” (manufactured by Nagase ChemteX Corporation).

  Examples of the dimer acid-modified epoxy resin include dimer acid glycidyl-modified compounds, reaction products of dimer acid and bisphenol A diglycidyl ether, and the like. The dimer acid-modified epoxy resin is represented by the following formula (3). Examples of commercially available products include “jER871”, “jER872” (manufactured by Mitsubishi Chemical Corporation), “YD-171”, “YD-172” (manufactured by Nippon Steel Chemical Co., Ltd.), and the like.

〔式中、Ｒはグリシジル基、ビスフェノールＡ型ジグリシジルエーテル構造などが挙げられる。ｎはそれぞれ独立に３〜９の整数である。〕

[In the formula, R includes a glycidyl group, a bisphenol A-type diglycidyl ether structure, and the like. n is an integer of 3-9 each independently. ]

  As the alicyclic epoxy resin having an ester skeleton, “Celoxide 2021P” (3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, the following formula (4), manufactured by Daicel Corporation), “Celoxide” 2081 "," Celoxide 2000 "," Celoxide 3000 "and the like.

  The epoxy equivalent of the epoxy resin having an ester skeleton is not particularly limited, but is preferably 100 to 1000, more preferably 110 to 800, still more preferably 120 to 600, and particularly preferably 130 to 400. Thereby, the point which can improve a flexibility in the case of an adhesive film form, the crosslink density of hardened | cured material becomes sufficient, and the point which can improve heat resistance are excellent. In addition, epoxy equivalent (g / eq) is the mass of resin containing 1 equivalent of epoxy groups, and can be measured according to JIS K7236: 2001.

  The content of the epoxy resin having an ester skeleton in the resin composition is not particularly limited, but from the viewpoint of improving the flexibility of the sheet-like form of the resin composition and improving the peel strength. When the non-volatile component in a resin composition is 100 mass%, 2-15 mass% is preferable and 3-12 mass% is more preferable.

  In the resin composition of the present invention, an epoxy resin having an ester skeleton and another epoxy resin may be used in combination within the range where the effects of the present invention are exhibited. Examples of other epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, and naphthol type. Epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure , Alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy Resins. Especially, it is preferable to use together the epoxy resin which has ester skeleton, and a biphenyl type epoxy resin from a viewpoint of the improvement of peel strength. These may be used alone or in combination of two or more.

  In the case of using an epoxy resin having an ester skeleton in combination with another epoxy resin as an epoxy resin, from the viewpoint of obtaining the flexibility of the sheet-like form, when the solid content of the entire epoxy resin is 100 parts by mass, the ester skeleton is The epoxy resin is preferably 10 to 100 parts by mass, more preferably 15 to 90 parts by mass, and still more preferably 20 to 80 parts by mass.

<(B) Active ester type curing agent>
The (B) active ester type curing agent used in the present invention is a compound having one or more active ester groups in one molecule, and can lower the dielectric loss tangent. Here, the “active ester group” means an ester group that reacts with an epoxy resin. The active ester type curing agent can react with the epoxy resin, and a compound having two or more active ester groups in one molecule is preferable. In general, a compound selected from the group consisting of phenol ester, thiophenol ester, N-hydroxyamine ester and heterocyclic hydroxy compound ester and having two or more ester groups with high reaction activity in one molecule is active. It is preferably used as an ester type curing agent.

  From the viewpoint of improving heat resistance, an active ester type curing agent obtained from a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound is more preferable. An active ester type curing agent obtained by reacting one or more selected from a phenol compound, a naphthol compound and a thiol compound with a carboxylic acid compound is more preferred. An aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferable. An aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and 2 in one molecule of the aromatic compound Particularly preferred are aromatic compounds having one or more active ester groups. The active ester type curing agent may be linear or hyperbranched. In addition, if the compound having at least two carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, it is heat resistant. Sexuality can be increased.

  Specific 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. Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred from the viewpoint of heat resistance. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

  Specific 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, tetrahydroxy Examples include benzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac. Among them, from the viewpoint of improving heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, phenol novolac are preferred, catechol, 1 , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophene Non-tetrahydrobenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak are more preferable. 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxy More preferred are hydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl diphenol, Phenol novolac is even more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthal Emissions, dicyclopentadienyl diphenol especially preferred, dicyclopentadienyl diphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol and triazinedithiol. The active ester type curing agent may be used alone or in combination of two or more.

  Specific examples of the active ester type curing agent include an active ester type curing agent containing a dicyclopentadienyl diphenol structure, an active ester type curing agent containing a naphthalene structure, and an active ester type curing containing a phenol novolac acetylated product. An active ester type curing agent containing a benzoylated product of a phenol novolac is preferable, and an active ester type curing agent containing a naphthalene structure and an active ester type curing agent containing a dicyclopentadienyl diphenol structure are more preferable. Commercially available products include EXB9451, EXB9460, EXB9460S, HPC8000-65T (manufactured by DIC Corporation) as an active ester type curing agent containing a dicyclopentadienyl diphenol structure, and EXB9416 as an active ester type curing agent containing a naphthalene structure. -70BK (manufactured by DIC Corporation), DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester type curing agent containing an acetylated product of phenol novolak, YLH1026 (Mitsubishi Chemical) as an active ester type curing agent containing a benzoylated phenol novolac Etc.).

  More specifically, an active ester type curing agent containing a dicyclopentadienyl diphenol structure includes a compound represented by the following formula (5).

（式中、Ｒはフェニル基、ナフチル基であり、ｋは０又は１を表し、ｎは繰り返し単位の平均で０．０５〜２．５である。）

(In the formula, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n is 0.05 to 2.5 on the average of repeating units.)

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

  The content of the active ester type curing agent is 1 to 30 when the nonvolatile component in the resin composition is 100% by mass from the viewpoint that the peel strength can be improved while reducing the dielectric loss tangent of the cured product. It is preferable that it is mass%, it is more preferable that it is 1.5-20 mass%, and 2-10 mass% is further more preferable.

  In the resin composition of this invention, you may add hardening | curing agents, such as a phenol type hardening | curing agent and a cyanate ester type hardening | curing agent, as needed in the range by which the effect of this invention is exhibited. When the solid content of the entire curing agent is 100 parts by mass, the total amount of the active ester type curing agent is preferably 30 to 100 parts by mass, and more preferably 50 to 100 parts by mass.

  In the resin composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, the ratio of the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent is: 1: 0.2-1: 2 is preferable, 1: 0.3-1: 1.5 is more preferable, and 1: 0.4-1: 1 is still more preferable. The total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive group of the curing agent. The total number of is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.

<(C) Inorganic filler>
The resin composition of this invention can reduce a dielectric loss tangent and a thermal expansion coefficient by containing an inorganic filler. The inorganic filler is not particularly limited. For example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate , Barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Of these, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable. In particular, fused silica and spherical silica are more preferable in terms of reducing the surface roughness of the insulating layer. Preferably, spherical fused silica is more preferable. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs Co., Ltd.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, and more preferably 2 μm or less from the viewpoint that the surface of the insulating layer has low roughness and enables fine wiring formation. Is more preferably 1 μm or less, still more preferably 0.8 μm or less, particularly preferably 0.6 μm or less, and particularly preferably 0.4 μm or less. On the other hand, when the resin composition is a resin varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. 05 μm or more is more preferable, 0.07 μm or more is further more preferable, and 0.1 μm or more is particularly preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  In view of reducing the dielectric loss tangent and preventing cracks in the multilayer printed wiring board, the content of the inorganic filler is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. Since the resin composition of this invention is excellent in the flexibility of a sheet form form, content of an inorganic filler can be 60 mass% or more or 70 mass% or more. On the other hand, 90 mass% or less is preferable, 85 mass% or less is more preferable, and 80 mass% or less is still more preferable from the point which prevents hardened | cured material from becoming weak and the point which prevents a peeling strength fall.

  In addition, the epoxy resin having an inorganic filler and an ester skeleton prevents the decrease in peel strength and increases the flexibility of the sheet-like form when (C) the inorganic filler is 100 parts by mass, (A ) The epoxy resin having an ester skeleton is 1 to 20 parts by mass, preferably 2 to 17 parts by mass, more preferably 3 to 14 parts by mass, and still more preferably 4 to 10 parts by mass.

  The inorganic filler is preferably surface-treated with a surface treatment agent. Specifically, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a styrylsilane coupling agent, and an acrylate silane. One or more surface treatments selected from a series coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, a vinyl silane coupling agent, a silane coupling agent, an organosilazane compound and a titanate coupling agent More preferably, the surface treatment is performed with an agent. Thereby, the dispersibility and moisture resistance of an inorganic filler can be improved.

  Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-glycidyloxypropyltrimethoxysilane , 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane Coupling agents, styrylsilane coupling agents such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyl Acrylate silane coupling agents such as triethoxysilane and 3-methacryloxypropyldiethoxysilane, and isocyanates such as 3-isocyanatopropyltrimethoxysilane Silane coupling agents, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacloxy Silane coupling agents such as propyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexa Phenyldisilazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1 3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldi Organos such as silazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane Silazane compound, tetra-n-butyl titanate dimer, titanium-i-propoxy octylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy Cis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate Tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, Isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, Titanate coupling agents such as propyldimethacrylisostearoyl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-amidoethyl / aminoethyl) titanate, etc. Is mentioned. Of these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are preferred. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ" manufactured by Shin-Etsu Chemical Co., Ltd. -31 "(hexamethyldisilazane) and the like.

  The amount of the surface treatment agent when the inorganic filler is surface-treated with the surface treatment agent is not particularly limited, but the surface treatment agent is 0.05 to 5 parts by mass with respect to 100 parts by mass of the inorganic filler. It is preferable to treat, more preferably 0.1 to 4 parts by mass, and more preferably 0.2 to 3 parts by mass, and more preferably 0.3 to 2 parts by mass. Is even more preferred.

  Moreover, in the inorganic filler surface-treated with the surface treatment agent, the presence of carbon atoms is confirmed by analyzing the surface composition of the inorganic filler, and the amount of carbon per unit surface area of the inorganic filler is obtained. be able to. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

The amount of carbon per unit surface area of the inorganic filler is 0.05 mg / square in terms of improving the dispersibility of the inorganic filler and stabilizing the arithmetic average roughness and the root mean square roughness after the wet roughening step of the cured product. m ² or more preferably, 0.1 mg / ^{m 2} or more, and further preferably 0.15 mg / ^{m 2} or more, 0.2 mg / ^{m 2} or more is even more preferred. On the other hand, in terms of preventing an increase in the melt viscosity at the melt viscosity and the adhesive film forms of the resin varnish is preferably 1 mg / ^{m 2} or less, more preferably 0.75 mg / ^{m 2} or less, 0.5 mg / ^{m 2} or less Is more preferable.

  The inorganic filler surface-treated with the surface treatment agent is preferably added to the resin composition after the inorganic filler is surface-treated with the surface treatment agent. In this case, the dispersibility of the inorganic filler can be further enhanced.

  The surface treatment method for the inorganic filler surface-treated with the surface treatment agent is not particularly limited, and examples thereof include a dry method and a wet method. As a dry method, an inorganic filler is charged in a rotary mixer, and an alcohol solution or an aqueous solution of a surface treatment agent is dropped or sprayed while stirring, followed by further stirring and classification with a sieve. Thereafter, the surface treatment agent and the inorganic filler can be dehydrated and condensed by heating. As a wet method, a surface treatment agent is added while stirring a slurry of an inorganic filler and an organic solvent, and after stirring, classification is performed by filtration, drying, and sieving. Thereafter, the surface treatment agent and the inorganic filler can be dehydrated and condensed by heating. Furthermore, an integral blend method in which a surface treating agent is added to the resin composition is also possible.

  One preferred embodiment of the resin composition of the present invention is to provide a resin composition having a low dielectric loss tangent of a cured product of the resin composition, a high peel strength, and an excellent flexibility in a sheet form. From the point, it is a resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester type curing agent, and (C) an inorganic filler, and 100% by mass of the nonvolatile component in the resin composition When (C) inorganic filler content is 50 mass% or more, and (C) inorganic filler is 100 mass parts, (A) 1-20 mass parts of epoxy resin having an ester skeleton (A) An epoxy resin having an ester skeleton and another epoxy resin are used in combination, and (A) a glycidyl ester type epoxy resin (more preferably diglycidyl phthalate) as an epoxy resin having an ester skeleton. Steal type epoxy resin or hexahydrophthalic acid diglycidyl ester type epoxy resin), biphenyl type epoxy resin as other epoxy resin, and silica as inorganic filler (more preferably, average particle size 0.01- An embodiment of a resin composition containing 5 μm silica) is preferred.

<(D) Curing accelerator>
When the resin composition of the present invention further contains a curing accelerator, the epoxy resin and the curing agent can be efficiently cured. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, a metal hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.

  The amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl). And amine compounds such as phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a guanidine type hardening accelerator, Dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , Diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl Rubiguanido, 1-(o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.

  The imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium tri Meritate 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2 '-Undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1 Dodecyl-2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a phosphonium type hardening accelerator, Triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. You may use these 1 type or in combination of 2 or more types.

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

  When mix | blending a hardening accelerator with the resin composition of this invention, the range of 0.005-1 mass part is preferable when the sum total of an epoxy resin and a hardening | curing agent is 100 mass parts, 0.01-0. The range of 5 parts by mass is more preferable. Within this range, thermosetting can be performed more efficiently, and the storage stability of the resin varnish is improved.

<(E) polymer resin>
When the resin composition of the present invention further contains (E) a polymer resin, the mechanical strength of the cured product can be improved, and further the film molding ability when used in the form of an adhesive film is improved. You can also. (E) As polymer resin, phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester Examples of the resin include phenoxy resin and polyvinyl acetal resin. These may be used alone or in combination of two or more. (E) The weight average molecular weight of the polymer resin is preferably in the range of 8000 to 200000, more preferably in the range of 12000 to 100,000, and still more preferably in the range of 20000 to 60000. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  When (E) polymer resin is mix | blended with the resin composition of this invention, 0.1-10 mass% is preferable when the non-volatile component in a resin composition is 100 mass%, 0.5-5 The mass% is more preferable. Within this range, the effect of improving the film forming ability and mechanical strength can be exhibited, and the melt viscosity can be increased and the roughness of the insulating layer surface after the wet roughening step can be reduced.

<Other ingredients>
In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Other components include thermosetting resins such as vinyl benzyl compounds, acrylic compounds, maleimide compounds, and blocked isocyanate compounds, organic fillers such as silicon powder, nylon powder, fluorine powder, and rubber particles; Adhesives, silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and other colorants, phosphorus compounds, metal hydroxides And flame retardants.

  The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. It can be adjusted by doing. Moreover, the said component may be melt | dissolved in the organic solvent and you may add in a resin composition, and it can also adjust as a resin varnish by adding an organic solvent further in a resin composition.

  In the present invention, since the dielectric loss tangent of the cured product of the resin composition is low, the peel strength is high, and a resin composition excellent in flexibility of the sheet form can be provided. It can be suitably used as a resin composition for an insulating layer of a multilayer printed wiring board. Furthermore, it can be suitably used as a resin composition for forming a conductor layer by plating (resin composition for an insulating layer of a multilayer printed wiring board on which a conductor layer is formed by plating), and further building a multilayer printed wiring board It is suitable as a resin composition for an up layer.

  The dielectric loss tangent of the cured product of the resin composition of the present invention can be grasped by the measurement method described in [Measurement of dielectric loss tangent] described later. The dielectric loss tangent is preferably 0.007 or less from the viewpoint of reducing electric signal loss. The lower the dielectric loss tangent, the better. There is no particular lower limit, but generally it is 0.002 or more, 0.003 or more, and the like.

  The resin composition of the present invention is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductor layer and the insulating layer obtained by plating is described later in [Plating conductor layer drawing]. It can be grasped by the measuring method described in [Measurement of Peeling Strength (Peel Strength)]. The peel strength is preferably 0.45 kgf / cm or more, more preferably 0.5 kgf / cm or more, and further preferably 0.55 kgf / cm or more in order to keep the insulating layer and the conductor layer in close contact with each other. The upper limit of the peel strength is preferably as high as possible and is not particularly limited, but is generally 1.5 kgf / cm or less, 1.2 kgf / cm or less, 1.0 kgf / cm or less, 0.8 kgf / cm or less.

  The glass transition temperature of the resin composition of this invention can be grasped | ascertained by the measuring method as described in [Measurement of glass transition temperature] described later. The glass transition temperature is preferably 150 ° C. or higher and more preferably 155 ° C. or higher from the viewpoint of improving heat resistance. Although there is no particular upper limit, it is generally 300 ° C. or lower.

  The resin composition of the present invention is a composition particularly suitable as a resin composition for an insulating layer of a multilayer printed wiring board. However, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a component filling It can be used in a wide range of applications where a resin composition is required, such as a resin. In addition, the form of the resin composition of the present invention is not particularly limited, but it can be applied to sheet-like laminated materials such as adhesive films and prepregs, and circuit boards (for laminated boards and multilayer printed wiring boards). The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. . 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>
(Adhesive film)
The adhesive film of the present invention has a resin composition layer formed on a support, and is prepared by a method known to those skilled in the art, for example, a resin varnish in which a resin composition is dissolved in an organic solvent. Can be produced by applying the composition to a support using a die coater or the like, and further drying the organic solvent by heating or blowing hot air to form a resin composition layer.

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

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

  The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of thinning, 15 to 80 μm is more preferable.

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

  Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

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

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

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

  First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

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

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

Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The pressing condition is that the degree of vacuum is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in the range of 1 to 15 kgf / cm 2, and the second stage press has the temperature of 150 to 200 ° C. and the pressure is in the range of 1 to 40 kgf / cm 2 It is preferred to do so. The time for each stage is preferably 30 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

  Next, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. For example, the drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary, but drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common. Is the method. If the support is not peeled off before drilling, it will be peeled off here.

  Next, a roughening process is performed on the surface of the insulating layer. In the case of dry-type roughening treatment, plasma treatment or the like can be mentioned. It is done. The wet roughening treatment is preferable in that smear in the via hole can be removed while forming an uneven anchor on the surface of the insulating layer. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth P) and Swelling Dip Securiganth SBU (ABUTEC Japan). be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages It becomes a printed wiring board. In the present invention, since it has low roughness and high peel, it can be suitably used as a build-up layer of a multilayer printed wiring board.

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

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

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Part” means part by mass.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

[Preparation of peel strength measurement sample]
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by etching 1 μm with CZ8100 manufactured by MEC Co., Ltd.

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

(3) Curing of the resin composition After peeling the polyethylene terephthalate (PET) film from the laminated adhesive film, the resin composition is cured under curing conditions of 100 ° C for 30 minutes and then at 180 ° C for 30 minutes. Formed

(4) Roughening treatment The inner layer circuit board on which the insulating layer is formed is a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) of Atotech Japan Co., Ltd. And soaking at 60 ° C. for 10 minutes. Next, as a roughening liquid, it was immersed in the concentrate compact P (KMnO4: 60g / L, NaOH: 40g / L aqueous solution) of Atotech Japan Co., Ltd. for 20 minutes at 80 ° C. Finally, as a neutralizing solution, it was immersed for 5 minutes at 40 ° C. in Reduction Sholysin Securigant P (an aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. Thereafter, it was dried at 80 ° C. for 30 minutes.

(5) Plating by semi-additive method This substrate was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. After annealing for 30 minutes at 150 ° C., an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 190 ° C. for 60 minutes. This substrate was used as an evaluation substrate.

[Measurement of peel strength (peel strength) of plated conductor layer]
In the conductor layer of the evaluation board, cut a portion of width 10 mm and length 100 mm, peel off one end, and hold it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50C-SL). The load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured.

[Measurement of dielectric loss tangent]
The adhesive films obtained in each Example and each Comparative Example were thermally cured at 190 ° C. for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, and a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technology Co., Ltd. were used. The dielectric loss tangent (tan δ) was measured by the cavity resonance method at a measurement frequency of 5.8 GHz. Two test pieces were measured, and the average value was calculated.

[Measurement of glass transition temperature]
The adhesive films obtained in each Example and each Comparative Example were heated at 190 ° C. for 90 minutes to thermally cure the resin composition layer. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The glass transition temperature was calculated in the second measurement.

[Evaluation of flexibility]
The adhesive films obtained in each Example and each Comparative Example were bent at 90 degrees, and the coating film surface was observed. The surface condition at that time was judged according to the following criteria.
○: No cracks were found on the coating film surface ×: Minute cracks were found on the coating film surface

<Example 1>
10 parts of a glycidyl ester type epoxy resin (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154), 15 parts of a crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) , 15 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000L”, epoxy equivalent 269), phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation), 1: 1 of MEK and cyclohexanone having a solid content of 30% by mass 10 parts of the solution was dissolved in 20 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of a 2-methoxypropanol solution having a solid content of 50% in a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” hydroxyl group equivalent 151 manufactured by DIC Corporation), active ester type curing 10 parts of an agent (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass having an active group equivalent of about 223), a curing accelerator (4-dimethylaminopyridine, a MEK solution having a solid content of 10% by mass) 1 part, spherical silica surface treated with phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, “SOC2” manufactured by Admatex Co., Ltd.) per unit area Of carbon of 0.39 mg / m ² ) was mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. Next, the resin varnish is uniformly applied on the release surface of a polyethylene terephthalate film with a release treatment (“PET501010” manufactured by Lintec Corporation, thickness 50 μm) so that the thickness of the resin composition layer after drying is 30 μm. It apply | coated and dried at 80-120 degreeC (average 100 degreeC) for 4 minutes, and produced the adhesive film.

<Example 2>
10 parts of the glycidyl ester type epoxy resin of Example 1 (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) was added to the glycidyl ester type epoxy resin (“EX-722L” manufactured by Nagase ChemteX Corporation), Epoxy equivalent 151) An adhesive film was produced in the same manner as in Example 1 except that the equivalent was changed to 10 parts.

<Example 3>
10 parts of the glycidyl ester type epoxy resin (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) of Example 1 was added to the glycidyl ester type epoxy resin (“YD172” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), epoxy equivalent. 600) An adhesive film was produced in the same manner as in Example 1 except that the amount was changed to 10 parts.

<Example 4>
10 parts of a glycidyl ester type epoxy resin (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) of Example 1 was added to a glycidyl ester type epoxy resin (“jER872” manufactured by Mitsubishi Chemical Corporation), a general formula ( An adhesive film was prepared in exactly the same manner as in Example 1 except that R in 3) was changed to 10 parts of bisphenol A type diglycidyl ether structure, epoxy equivalent 650).

<Example 5>
The glycidyl ester type epoxy resin of Example 1 (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) was changed to 10 parts, and further a crystalline bifunctional epoxy resin (manufactured by Mitsubishi Chemical Corporation). “YX4000HK”, epoxy equivalent 185) An adhesive film was produced in the same manner as in Example 1 except that 15 parts were changed to 0 parts.

<Example 6>
Alicyclic epoxy resin having an ester skeleton ("Celoxide 2021P" manufactured by Daicel Corporation, epoxy equivalent 126) 8 parts, dicyclopentadiene type epoxy resin ("HP-7200H" manufactured by DIC Corporation, epoxy equivalent 275) 12 10 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass) was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 35 parts of an active ester-type curing agent (“HPC8000-65T” manufactured by DIC Corporation, 65% by weight non-volatile toluene solution having an active group equivalent of about 223), a curing accelerator (4-dimethyl) 2.4 parts of aminopyridine, MEK solution having a solid content of 5% by weight, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa- 10 parts of phosphaphenanthrene-10-oxide (average particle size 2 μm), spherical silica (average particle size) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 150 μm of 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., and carbon amount of 0.39 mg / m ² per unit area were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was produced in the same manner as in Example 1.

<Comparative Example 1>
10 parts of the glycidyl ester type epoxy resin of Example 1 (“EX-721” manufactured by Nagase ChemteX Corporation, epoxy equivalent 154) was added to bisphenol A type epoxy resin (“828 US” manufactured by Mitsubishi Chemical Corporation), epoxy equivalent 180 ) An adhesive film was produced in the same manner as in Example 1 except that the content was changed to 10 parts.

<Comparative example 2>
10 parts of the triazine skeleton-containing phenol resin of Example 1 (“LA3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution of 50% non-volatile component having a hydroxyl group equivalent of 151) was changed to 20 parts, and further active ester type curing The adhesive film was prepared in the same manner as in Example 1 except that 10 parts of the agent (“PCC8000-65T” manufactured by DIC Corporation, toluene solution with a non-volatile content of 65 mass% having an active group equivalent of about 223) was changed to 0 parts. Produced.

<Comparative Example 3>
The glycidyl ester type epoxy resin of Example 1 (“EX-721” manufactured by Nagase ChemteX Corp., epoxy equivalent 154) was changed to 35 parts, and further a crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Co., Ltd.). “Epoxy equivalent 185) 15 parts in Example 1 except that 15 parts were changed to 0 parts and 15 parts in biphenyl type epoxy resin (“ NC3000L ”, Epoxy equivalent 269 manufactured by Nippon Kayaku Co., Ltd.) were changed to 5 parts. An adhesive film was prepared in the same manner as described above.

  The results are shown in Table 1.

  From the results shown in Table 1, it can be seen that the resin compositions of the examples have a low dielectric loss tangent of the cured product, a high peel strength, and excellent flexibility in the sheet form. On the other hand, in Comparative Example 1, since an epoxy resin having an ester skeleton is not used, the dielectric loss tangent is increased and the flexibility is also inferior. In Comparative Example 2, since the active ester type curing agent is not used, the dielectric loss tangent is remarkably increased. In Comparative Example 3, the amount of the epoxy resin having an ester skeleton is large, and the peel strength is lowered.

Claims (9)

(A) An epoxy resin having an ester skeleton, (B) an active ester type curing agent (excluding an active ester curing agent containing a phosphorus atom) and (C) a resin composition containing an inorganic filler Formed sheet-like laminated material,
When the nonvolatile component in the resin composition is 100% by mass, the content of the (C) inorganic filler is 50% by mass or more,
(C) When the inorganic filler is 100 parts by mass, (A) the epoxy resin having an ester skeleton is 1 to 20 parts by mass,
(A) component is selected from phthalic acid diglycidyl ester type epoxy resin, hexahydrophthalic acid diglycidyl ester type epoxy resin, dimer acid-modified epoxy resin, and alicyclic epoxy resin,
The epoxy equivalent of (A) component is 100-1000, The sheet-like laminated material characterized by the above-mentioned.   (C) The sheet-like laminated material according to claim 1, wherein the inorganic filler has an average particle diameter of 0.01 to 5 μm. (A) An epoxy resin having an ester skeleton and another epoxy resin are used in combination,
(A) As an epoxy resin having an ester skeleton, phthalic acid diglycidyl ester type epoxy resin or hexahydrophthalic acid diglycidyl ester type epoxy resin,
Including biphenyl type epoxy resin as other epoxy resin,
(C) The sheet-like laminated material according to claim 1 or 2, comprising silica having an average particle diameter of 0.01 to 5 µm as an inorganic filler.   Furthermore, (D) Sheet-like laminated material of any one of Claims 1-3 containing a hardening accelerator.   The sheet-like laminated material according to any one of claims 1 to 4, further comprising (E) a polymer resin.   It is a sheet-like laminated material for buildup layers of a multilayer printed wiring board, The sheet-like laminated material of any one of Claims 1-5.   It is an adhesive film or a prepreg, The sheet-like laminated material of any one of Claims 1-6.   The multilayer printed wiring board by which the sheet-like laminated material of any one of Claims 1-7 was thermoset, and the insulating layer was formed.   A semiconductor device using the multilayer printed wiring board according to claim 8.