JP2014017301A - Insulation resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulation resin sheet which is excellent in a via shape, thin film insulation reliability, surface smoothness and embedding properties.SOLUTION: An etching amount of a specific first layer and a specific second layer is controlled in an insulation resin sheet having a support layer, the specific first layer and the specific second layer.

Description

  The present invention relates to an insulating resin sheet. Furthermore, it is related with the multilayer printed wiring board and semiconductor device containing the said insulating resin sheet.

  In recent years, electronic devices are becoming smaller and higher performance. In multilayer printed wiring boards, conductor wiring has been miniaturized and miniaturized to improve the mounting density of electronic components. Under such circumstances, as a method for producing a multilayer printed wiring board, a build-up method in which circuit-formed conductor layers and insulating layers (interlayer insulating layers) are alternately stacked is widely used. For the formation of fine conductor wiring, an additive method is usually adopted, and a semi-additive method is mainly used.

 On the other hand, Patent Document 1 describes that the resin composition layer is formed into multiple layers and each layer has a different function. However, it is difficult to stabilize the quality, for example, the layers are mixed. . In Patent Document 2, an insulating resin sheet having a cured product layer and an adhesive layer is disclosed, but no mention is made regarding the via shape for drilling.

Republished 2008-90835 JP 2010-28036

 In order to improve the performance of the multi-layered film, the present inventors made various studies and manufactured a multilayer printed wiring board. In a multi-layered film, due to the difference in properties of each layer. During laser processing, it was difficult to adjust energy, and a step was generated in the vias of each layer, resulting in a new problem that the via shape became distorted. As a result of intensive studies, the present inventors have found that the problem of via shape can be solved by controlling the etching amount of each layer.

 The present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is to provide an insulating resin sheet excellent in via shape, thin film insulation reliability, surface smoothness and embedding property. is there.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a support layer, a specific first layer formed on the support, and a specific second layer formed on the first layer. The present invention has been completed by controlling the etching amount of the first layer and the second layer in the insulating resin sheet having the layers.

The present invention includes the following contents.
[1] A support and a first layer containing an epoxy resin, a curing agent and an inorganic filler formed on the support, wherein the elastic modulus of the first layer is 0.5 GPa or more, A first layer having a thickness of 2 to 18 μm, and a second layer formed on the first layer and containing an epoxy resin, a curing agent and an inorganic filler, wherein the second layer And a second layer having a second melt thickness of 10 to 120 μm, and an etching amount (E1) per unit area of the first layer and the second layer. The insulating resin sheet, wherein the etching amount (E2) per unit area of the layer is expressed by E1 / E2 = 0.3-3.
[2] The insulating resin sheet according to [1], wherein the elastic modulus of the first layer is 0.5 GPa or more and 10 GPa or less.
[3] The insulating resin sheet according to [1] or [2], wherein the thickness of the first layer is 2 to 8 μm.
[4] The epoxy resin in the first layer contains one or more selected from naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and naphthylene ether type epoxy resin [1] ] The insulating resin sheet according to any one of [3] to [3].
[5] The insulating resin sheet according to any one of [1] to [4], wherein an average particle diameter of the inorganic filler in the first layer is 0.01 to 0.8 μm.
[6] The insulating resin sheet according to any one of [1] to [5], wherein the second layer has a minimum melt viscosity of 100 to 5000 poise.
[7] The insulating resin sheet according to any one of [1] to [6], wherein the second layer has a thickness of 15 to 100 μm.
[8] Any of [1] to [7], wherein when the resin component in the second layer is 100% by mass, the liquid epoxy resin in the second layer is 1 to 35% by mass. The insulating resin sheet as described.
[9] The insulating resin sheet according to any one of [1] to [8], wherein the inorganic filler in the second layer is surface-treated with a surface treatment agent.
[10] The insulating resin sheet according to any one of [1] to [9], wherein a total thickness of the first layer and the second layer is 15 to 120 μm.
[11] The insulating resin sheet according to any one of [1] to [10], wherein the first layer and the second layer are made of different materials.
[12] The etching amount (E1) per unit area of the first layer and the etching amount (E2) per unit area of the second layer are E1 / E2 = 0.5-2. The insulating resin sheet according to any one of [1] to [11].
[13] The insulating resin sheet according to any one of [1] to [12], which is an insulating resin sheet for a buildup layer of a multilayer printed wiring board.
[14] (A) A step of laminating the insulating resin sheet according to any one of [1] to [13] on one side or both sides of the inner layer circuit board, (B) forming the insulating layer by thermosetting the insulating resin sheet. A step, (C) a step of peeling the support, (D) a step of drilling the insulating layer to form a blind via, (E) a step of roughening the surface of the insulating layer, (F) after the roughening treatment A method of manufacturing a multilayer printed wiring board, comprising: plating a surface of an insulating layer to form a conductor layer, wherein (D) forming a blind via by drilling the insulating layer; 1 to 6 mJ, and in the step of (R) roughening the surface of the insulating layer, a roughening treatment with an oxidizing agent is performed at 60 to 80 ° C. for 10 to 30 minutes. Method.
[15] In the step of roughening the surface of the insulating layer (E), a swelling treatment is performed at 50 to 80 ° C. for 5 to 20 minutes, followed by a water washing treatment, followed by a roughening treatment with an oxidizing agent. [14] The method for producing a multilayer printed wiring board according to [14].
[16] A semiconductor device using a multilayer printed wiring board manufactured by the method according to [14] or [15].

 In an insulating resin sheet having a support, a specific first layer formed on the support, and a specific second layer formed on the first layer, the first layer and the second layer By controlling the etching amount, an insulating resin sheet excellent in via shape, thin film insulation reliability, surface smoothness and embedding property can be provided.

[Insulating resin sheet]
The insulating resin sheet of the present invention is a first layer containing a support and an epoxy resin, a curing agent and an inorganic filler formed on the support, and the elastic modulus of the first layer is 0. A first layer having a thickness of 5 GPa or more and a thickness of the first layer of 2 to 18 μm, and a second layer containing an epoxy resin, a curing agent and an inorganic filler formed on the first layer, The second layer has a minimum melt viscosity of 100 to 19500 poise, and the second layer has a thickness of 10 to 120 μm. The etching amount per unit area of the first layer (E1 ) And the etching amount (E2) per unit area of the second layer are controlled by E1 / E2 = 0.3-3. In addition, you may have a protective film in the exposed surface side of a 2nd layer in order to prevent adhesion of refuse etc.

  In the insulating resin sheet of the present invention, the surface smoothness and via shape are improved by defining the elastic modulus and thickness of the first layer, and the embedding property and surface smoothness are defined by defining the minimum melt viscosity and thickness of the second layer. Property can be improved. Then, the etching amount per unit area of the first layer (E1) and the etching amount per unit area of the second layer (E2) are controlled to be E1 / E2 = 0.3 to 3, thereby generating after desmearing. The step difference between the first layer and the second layer is suppressed, and the via shape can be improved. Here, the etching amount is an index of the degree of roughening of the cured product with respect to the desmear treatment, and the desmear treatment is performed by controlling the etching amount to E1 / E2 = 0.3-3, preferably 0.5-2. At times, the difference in the degree of roughening between the first layer and the second layer can be reduced to achieve a good via shape. Therefore, the interlayer conductive reliability of the multilayer printed wiring board is excellent, and it is suitable as an insulating resin sheet for the insulating layer of the multilayer printed wiring board. Furthermore, it can be more suitably used as an insulating resin sheet for build-up layers of multilayer printed wiring boards and an insulating resin sheet for forming a conductor layer by plating.

[Support]
Examples of the support of the present invention include plastic films and metal foils. Specifically, as the plastic film, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, acrylic, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone And polyimide. Among these, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and an inexpensive polyethylene terephthalate film is particularly preferable. Examples of the metal foil include copper foil and aluminum foil. From the viewpoint of versatility, a plastic film is preferable, and when a plastic film is used, it is preferable to use a support body on which the surface of the resin layer is release-treated in order to improve the peelability. The release agent used for the release treatment is not particularly limited as long as the resin layer can be peeled off from the support. For example, silicon release agent, alkyd resin release agent, polyolefin resin, urethane resin, fluorine Examples thereof include resins. In addition, you may use the plastic film with a release layer marketed as a preferable thing, For example, SK-1, AL which is a PET film which has a release layer which has an alkyd resin type release agent as a main component, for example -5, AL-7 (manufactured by Lintec Corporation) and the like. Further, the plastic film may be subjected to mat treatment or corona treatment, and a release layer may be formed on the treated surface. On the other hand, the metal foil can be removed by an etching solution, but the metal foil may be used as a conductor layer without being removed. Although the thickness of a support body is not specifically limited, The range of 10-150 micrometers is preferable and the range of 25-50 micrometers is more preferable.

  When it has a protective film, the plastic film similar to a support body can be used. The protective film may be subjected to a surface treatment such as a mud treatment or a corona treatment, or may be subjected to a mold release treatment similar to the above. As for the thickness of a protective film, 3-30 micrometers is preferable.

[Resin composition]
The first layer and the second layer of the present invention are formed by layering a resin composition. The resin composition can be used without particular limitation as long as it contains (a) an epoxy resin, (b) a curing agent, and (c) an inorganic filler. Further, a thermoplastic resin, a curing accelerator, and other components can be blended. Hereinafter, the blending components will be described.

(A) Epoxy resin Although it does not specifically limit as an epoxy resin used for this invention, It is preferable to contain the epoxy resin which has a 2 or more epoxy group in 1 molecule. Specifically, 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, naphthol type epoxy resin, naphthalene Type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, butadiene structure Epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halo Emissions epoxy resins. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of improving thin film insulation reliability, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type Epoxy resins, anthracene type epoxy resins, and epoxy resins having a butadiene structure are preferred. In particular, the epoxy resin in the first layer is a naphthol type epoxy resin, a naphthalene type epoxy resin, or a biphenyl type epoxy because the crosslink density when the first layer is thermally cured is lowered and the top shape of the via is improved. It is more preferable to contain one or more selected from resins and naphthylene ether type epoxy resins. Specifically, for example, bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), Naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS”, “EXA4032SS” manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), Naphthol type epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), epoxy resin having butadiene structure (“PB-3600” manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having biphenyl structure (Nipponization) “NC3000H”, “NC3000L”, “NC31” manufactured by Yakuhin Co., Ltd. "00", "YX4000", "YX4000H", "YX4000HK", "YL6121") manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin (DIC) “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3”), glycidyl ester type epoxy resin (“EX711”, “EX721” manufactured by Nagase ChemteX Corp.) ("R540" manufactured by Printec Co., Ltd.).

  An epoxy resin can improve embedding property by including a liquid epoxy resin. Furthermore, it is preferable to use a liquid epoxy resin and a solid epoxy resin in combination. The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and a liquid at a temperature of 20 ° C. The solid epoxy resin has three or more epoxy groups in one molecule. And an aromatic epoxy resin that is solid at a temperature of 20 ° C. is preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the blending ratio (liquid epoxy resin: solid epoxy resin) is 1: The range of 0.1 to 1: 2 is preferable, the range of 1: 0.3 to 1: 1.8 is more preferable, and the range of 1: 0.6 to 1: 1.5 is still more preferable.

  The liquid epoxy resin is preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, glycidyl ester type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene. A type epoxy resin is more preferable. You may use these 1 type or in combination of 2 or more types. Solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, biphenyl type epoxy resins, and naphthylene ethers. Type epoxy resin is preferable, and naphthol type epoxy resin and biphenyl type epoxy resin are more preferable. You may use these 1 type or in combination of 2 or more types.

  In the resin composition of the present invention, from the viewpoint of improving thin film insulation reliability of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the content of the epoxy resin is 3 to 40. It is preferably mass%, more preferably 5 to 35 mass%, still more preferably 10 to 30 mass%. In particular, when the resin component in the second layer is 100% by mass in terms of improving the embedding property of the second layer, the content of the liquid epoxy resin in the second layer is preferably 1 to 35% by mass, 3-30 mass% is more preferable, and 6-25 mass% is still more preferable.

(B) Curing agent The curing agent used in the present invention is not particularly limited, but includes a phenolic curing agent, an active ester curing agent, a cyanate ester curing agent, a benzoxazine curing agent, an acid anhydride curing agent, and the like. It is preferable to use one or more selected from phenolic curing agents, active ester curing agents and cyanate ester curing agents. These may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as a phenol type hardening | curing agent, A biphenyl type hardening | curing agent, a naphthalene type hardening | curing agent, a phenol novolak type hardening | curing agent, a naphthylene ether type hardening | curing agent, and a triazine skeleton containing phenol type hardening | curing agent are preferable. Specifically, biphenyl type curing agents MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation), phenol novolac type curing agent TD2090 (manufactured by DIC Corporation), Examples include naphthylene ether type curing agent EXB-6000 (manufactured by DIC Corporation). Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation) and the like. In particular, naphthalene type curing agents and triazine skeleton-containing phenolic curing agents are more suitable.

Active ester-based curing agents generally include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds. Is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. 1 type (s) or 2 or more types can be used for an active ester type hardening | curing agent. Specifically, an active ester curing agent having a dicyclopentadienyl diphenol structure, an active ester curing agent having a naphthalene structure, an active ester curing agent that is an acetylated product of phenol novolac, and a benzoylated phenol novolac A certain active ester type curing agent is preferable, and in particular, an active ester type curing agent containing a dicyclopentadienyl diphenol structure in that the melt viscosity of the resin composition layer can be lowered and embedding property can be improved. Is more preferable. Commercially available products include those containing a dicyclopentadienyl diphenol structure, EXB9451, EXB9460, EXB9460S-65T, HPC
8000-65T (manufactured by DIC Corporation, active group equivalent of about 223), active ester-based curing agent that is an acetylated product of phenol novolak, DC808 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 149), benzoyl of phenol novolac YLH1026 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 200), YLH1030 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 201), YLH1048 (manufactured by Mitsubishi Chemical Corporation), Active group equivalent of about 245) and the like.

 Although there is no restriction | limiting in particular as cyanate ester type hardening | curing agent, Novolac type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester curing agents, and prepolymers in which these are partially triazines. Although the weight average molecular weight of a cyanate ester hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether , Phenol novolac, Examples thereof include polyfunctional cyanate resins derived from resole novolac, dicyclopentadiene structure-containing phenol resins, prepolymers in which these cyanate resins are partially triazines, and these may be used alone or in combination of two or more. Examples of commercially available cyanate ester resins include phenol novolac polyfunctional cyanate ester resins (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and some or all of bisphenol A dicyanate are triazines and trimers. The prepolymer (Lonza Japan Co., Ltd. product, BA230, cyanate equivalent 232), dicyclopentadiene structure containing cyanate ester resin (Lonza Japan Co., Ltd. product, DT-4000, DT-7000) etc. are mentioned.

  The mixing ratio of the epoxy resin and the curing agent is preferably a ratio in which the number of reactive groups of the curing agent is in the range of 0.3 to 2.0 when the number of epoxy groups of the epoxy resin is 1, preferably 0.5 to 1.0. The ratio which becomes a range is more preferable. In addition, the number of epoxy groups of the epoxy resin present in the resin composition is a total value of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents.

(C) Inorganic filler Examples of the inorganic filler used in the present invention include silica, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, and titanium oxide, and silica and alumina are preferable. In particular, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable, and spherical silica and fused silica are more preferable. These can use 1 type (s) or 2 or more types. Spherical fused silica is more preferable from the viewpoint of improving the filling property into the resin composition. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs.

  The average particle size of the inorganic filler is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and even more preferably 0.6 μm or less, from the viewpoint of improving thin-film insulation reliability and surface smoothness. . On the other hand, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more from the viewpoint of improving the dispersibility of the inorganic filler. In particular, in order to improve the surface smoothness of the first layer, the average particle size of the inorganic filler in the first layer is preferably 0.01 to 0.8 μm, and more preferably 0.01 to 0.6 μm. 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.

  The content of the inorganic filler is 35 when the nonvolatile component in the resin composition is set to 100% by mass from the viewpoint of preventing the flexibility of the sheet form from decreasing and decreasing the linear thermal expansion coefficient. -85 mass% is preferable, and 40-75 mass% is more preferable.

  The inorganic filler is surface-treated with a surface treatment agent such as an epoxy silane coupling agent, an amino silane coupling agent, a mercapto silane coupling agent, a silane coupling agent, an organosilazane compound, or a titanate coupling agent. What improved the moisture resistance is preferable. You may use these 1 type or in combination of 2 or more types. Of these, aminosilane coupling agents are preferred because of their excellent moisture resistance, dispersibility, and properties of cured products. In particular, in order to improve the embedding property of the second layer, the inorganic filler in the second layer is preferably surface-treated with a surface treatment agent. 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., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. ”(Phenyltrimethoxysilane),“ SZ-31 ”(hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

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

  The polystyrene-reduced weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 70000, more preferably in the range of 10,000 to 60000, and still more preferably in the range of 20000 to 60000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 "," YL7482 ", etc. are mentioned.

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

  0.5-60 mass% is preferable with respect to 100 mass% of non-volatile components in a resin composition, and, as for content of a thermoplastic resin, 3-50 mass% is more preferable, and 5-40 mass% is still more preferable.

(E) Curing accelerator Examples of the curing accelerator include organic phosphine compounds, imidazole compounds, amine adduct compounds, and tertiary amine compounds. The content of the curing accelerator is preferably used in the range of 0.01 to 3% by mass when the total of the nonvolatile components of the epoxy resin and the curing agent is 100% by mass. A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

 In the resin composition of the present invention, flame retardants, rubber particles, organic solvents, and other additives can be appropriately blended.

  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. By doing so, it can be produced as a resin varnish.

[First layer]
The first layer of the present invention can be produced as a resin composition layer in which a resin composition is formed on a support. The resin composition layer can be formed, for example, by preparing a resin composition containing an organic solvent, applying the resin composition on a support, drying and heating. The drying and heating conditions are preferably 130 to 170 ° C. for 5 to 30 minutes, more preferably 140 to 160 ° C. for 5 to 20 minutes from the viewpoint of adjusting the elastic modulus and improving the productivity of the substrate.

 The elastic modulus of the first layer of the present invention is controlled to be 0.5 GPa or more. By doing in this way, the 1st layer and the 2nd layer are not mixed, and the outstanding insulating resin sheet can be produced. In particular, from the viewpoint of improving surface smoothness, 0.8 GPa or more is preferable, 1 GPa or more is more preferable, 1.5 GPa or more is further preferable, and 2 GPa or more is even more preferable. The upper limit is not particularly limited, but is generally 10 GPa or less and 5 GPa or less.

 The thickness of the 1st layer of this invention is controlled so that it may become 2-18 micrometers. By doing in this way, the insulating resin sheet excellent in surface smoothness and also excellent in the via shape can be produced. From the viewpoint of improving the surface smoothness, it is more preferably 3 μm or more, further preferably 4 μm or more. From the viewpoint of improving the via shape, it is preferably 16 μm or less, more preferably 14 μm or less, further preferably 12 μm or less, still more preferably 10 μm or less, and particularly preferably 8 μm or less.

[Second layer]
The second layer of the present invention can also be produced as a resin composition layer in which a resin composition is formed on a support using the same resin composition as described above. The resin composition layer can be formed, for example, by preparing a resin composition containing an organic solvent, applying the resin composition on a support, and drying. Drying conditions are preferably 80 to 120 ° C. and 3 to 15 minutes. As a resin composition, it is preferable to adjust so that a 1st layer and a 2nd layer may be comprised from a different material, Specifically, the content of the resin composition from which the kind of compounding component differs, and a compounding component differs Examples thereof include a resin composition. By doing so, characteristic performance can be imparted to each of the first layer and the second layer.

 The minimum melt viscosity of the second layer of the present invention is controlled to be 100 to 19500 poise. By doing in this way, the insulating resin sheet excellent in embedding property and surface smoothness can be produced. From the viewpoint of preventing air entrainment at the time of embedding, it is preferably 18000 poise or less, more preferably 15000 poise or less, still more preferably 10,000 poise or less, still more preferably 8000 poise or less, and even more preferably 5000 poise or less. From the viewpoint of preventing bleeding at the time of embedding, it is preferably 200 poise or more, more preferably 400 poise or more, still more preferably 600 poise or more, and even more preferably 800 or more.

 The thickness of the second layer of the present invention is controlled to be 10 to 120 μm. By doing in this way, the insulating resin sheet excellent in surface smoothness and embedding property can be produced, and it will be excellent also in thin film formation. From the viewpoint of improving the surface smoothness and the embedding property, 15 μm or more is preferable. From the viewpoint of improving the via shape, it is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 25 μm or less.

[Method for producing insulating resin sheet]
Various methods can be used as a method for manufacturing the insulating resin sheet. For example, a resin composition layer as a first layer can be formed on a support, a resin composition can be applied thereon, and a resin composition layer as a second layer can be formed by drying. Moreover, after producing what formed the resin composition layer which is the 1st layer on the support body, and what formed the resin composition layer which is the 2nd layer on another support body, respectively, each resin composition A method of laminating the layer surfaces by lamination is also mentioned. The conditions for laminating together are preferably a laminating temperature of 70 to 110 ° C., a laminating time of 5 to 30 seconds, and a laminating pressure of 1 to 10 kgf / cm ² .

 From the viewpoint of thinning, the total thickness of the first layer and the second layer of the present invention is preferably 15 to 120 μm, more preferably 20 to 60 μm, and still more preferably 20 to 40 μm. .

[Multilayer printed wiring board using insulating resin sheet]
Hereinafter, an example of the manufacturing method of the multilayer printed wiring board using the insulating resin sheet of this invention is explained in full detail.

 In the method for producing a multilayer printed wiring board of the present invention, (A) a step of laminating an insulating resin sheet on one or both sides of the inner circuit board, (B) a step of thermosetting the insulating resin sheet to form an insulating layer, (C) Step of peeling the support, (D) Step of drilling the insulating layer to form a blind via, (E) Step of roughening the surface of the insulating layer, (F) Insulating layer after the roughening treatment The process of plating on the surface and forming a conductor layer, etc. can be included.

 (A) In the step of laminating the insulating resin sheet on one side or both sides of the inner layer circuit board (step (A)), the second layer of the insulating resin sheet is placed on the inner layer circuit board side and laminated on one side or both sides of the inner layer circuit board To do. As used herein, the inner layer circuit board refers to a conductive layer patterned (circuit formed) on one or both sides of a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, or a thermosetting polyphenylene ether board. And an intermediate product in which an insulating layer and a conductor layer are to be formed when a multilayer printed wiring board is manufactured. In addition, it is preferable from the viewpoint of improving the adhesion between the insulating layer and the inner circuit board that the surface of the conductor layer has been previously roughened by blackening or the like.

In step (A), when the insulating resin sheet has a protective film, after removing the protective film, the insulating resin sheet and the inner circuit board are preheated as necessary, and the insulating resin sheet is pressurized and Crimp to the inner circuit board while heating. In the insulating resin sheet 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., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

 (B) In the step of forming the insulating layer by thermosetting the insulating resin sheet ((B) step), the insulating resin sheet is laminated on the inner circuit board, and then the first layer and the second layer are thermoset. An insulating layer (cured product) can be formed on the inner layer circuit board. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C. Further, by thermosetting without peeling off the support, it is possible to prevent adhesion of foreign matters such as dust and dust during thermosetting.

 (C) In the step of peeling the support (step (C)), the support is peeled off. When the substrate is a plastic film, the substrate can be peeled by mechanical removal with a manual or automatic peeling device. When the substrate is a metal foil, the metal foil can be peeled and removed by dissolving the metal foil with an etching solution or the like.

 (D) In the step of drilling the insulating layer to form blind vias (step (D)), the insulating layer is punched to form blind vias. The drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary. However, drilling by a laser such as a carbon dioxide laser or YAG laser is preferable and versatile. In view of the above, a carbon dioxide laser is more preferable. In addition, (D) process may be performed before (C) process, and may be performed after (C) process.

  When forming a blind via with a carbon dioxide laser, the number of shots is usually selected from 1 to 5 shots, although it depends on the depth and hole diameter of the blind via to be formed. In order to increase the processing speed of the blind via and improve the productivity of the multilayer printed wiring board, the number of shots is preferably small, and the number of shots is preferably 1 to 3. In addition, when processing with multiple shots, the burst mode, which is a continuous shot, is a multi-shot with a time interval because the processing heat is trapped in the hole and the via shape tends to be distorted. Is preferred.

  The pulse width of the carbon dioxide laser is not particularly limited, and can be selected in a wide range from a middle range of 28 μsec to a short pulse of 4 μsec. However, in the case of high energy, the short pulse is superior in the via processing shape.

 When drilling with a carbon dioxide laser, in the insulating resin sheet of the present invention, the laser energy is adjusted to 1 to 6 mJ from the viewpoint of suppressing the step between the first layer and the second layer and improving the via shape. It is preferable to adjust to 2 to 5 mJ.

  (E) In the step of roughening the surface of the insulating layer (step (E)), the surface of the insulating layer is roughened after peeling off the support. In the case of dry-type roughening treatment, plasma treatment and the like can be mentioned, and in the case of wet-type roughening treatment, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are performed in this order. It is done. The wet roughening treatment is preferable in that smear in the blind via can be removed while forming uneven anchors 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 commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth S) and Swelling Dip Securiganth SBU (ABUTEC Japan). be able to. Moreover, the via | veer shape can be maintained more favorable by performing a swelling process, performing a washing process after that, and performing the roughening process by an oxidizing agent after that.

  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.

  In the insulating resin sheet of the present invention, the etching amount (E1) per unit area of the first layer and the etching amount (E2) per unit area of the second layer are controlled to E1 / E2 = 0.3-3. This suppresses a step difference between the first layer and the second layer that occurs after desmearing, and makes it possible to improve the via shape. In particular, by adopting the roughening treatment conditions described above, it becomes easier to better control the via shape.

  (F) In the step of forming the conductor layer by plating on the surface of the insulating layer after the roughening treatment ((F step)), the conductor layer can be formed on the surface of the insulating layer. As a method for forming the plating, 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. As wet plating, a method of forming a conductor layer by combining electroless plating and electrolytic plating after the roughening treatment, a method of forming a plating resist having a pattern opposite to that of the conductor layer, and forming the conductor layer only by electroless plating , Etc. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

  By repeating the above-described series of steps a plurality of times, a multilayer printed wiring board in which build-up layers are laminated in multiple stages is obtained. In the present invention, since the conduction reliability between layers can be ensured by improving the via shape, it can be suitably used as an insulating resin sheet for a buildup layer of a multilayer printed wiring board.

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board manufactured by the method 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 Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In the following description, “part” means “part by mass”.

  First, measurement methods and evaluation methods in the physical property evaluation in this specification will be described.

<Evaluation of via shape>
(1) Substrate treatment of substrate Substrate on both sides of glass cloth base epoxy resin double-sided copper-clad laminate [copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works Ltd. R5715ES] on MEC CZ8100 The copper surface was roughened by dipping.
(2) Lamination of Insulating Resin Sheet Using the batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.), the second layer is copper-clad using the insulating resin sheets prepared in Examples and Comparative Examples. Lamination was performed so as to contact both sides of the laminate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
(3) Curing of resin composition After lamination, the resin composition was cured under curing conditions at 100 ° C for 30 minutes and then at 180 ° C for 30 minutes to form an insulating layer.
(4) Formation of blind vias After curing, the support was peeled off, and a blind via was formed on the first layer using a laser processing machine (a carbon dioxide laser device manufactured by Mitsubishi Electric Corporation: ML605GTWII-P). . The conditions of laser irradiation were as follows: pulse width 13 μs, energy 3 mJ, number of shots 1 shot, mask diameter 1.1 mm.
(5) Desmear treatment After the formation of blind vias, it is immersed in a swelling dip securigand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C. for 5 minutes, and then as a roughening liquid, Atotech Japan Soaked in Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, washed with water, and finally neutralized as a reduction of Atotech Japan Co., Ltd. It was immersed in Soleucine securigant P at 40 ° C. for 5 minutes. Then, it dried at 130 degreeC for 15 minutes. This removed smears in the blind vias.
(6) Observation of via The cross section of the via was observed with SEM. When the wall surface level difference between the first layer and the second layer is 5 μm or more, “×” is given, and when the wall level step is less than 5 μm but the via diameter is large, “△”, and the wall level step is less than 5 μm Those with no via diameter spread were marked with “◯”.

<Evaluation of thin film insulation reliability>
(1) Substrate substrate treatment Glass cloth base epoxy resin double-sided copper-clad laminate with inner layer circuit [copper foil thickness 18 μm, residual copper ratio 60%, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES ] Were immersed in CZ8100 manufactured by Mec Co., Ltd. to roughen the copper surface.
(2) Lamination of Insulating Resin Sheet Using the batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.), the second layer is copper-clad using the insulating resin sheets prepared in Examples and Comparative Examples. Lamination was performed so as to contact both sides of the laminate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.
(3) Curing of resin composition After lamination, the resin composition was cured under curing conditions at 100 ° C for 30 minutes and then at 180 ° C for 30 minutes to form an insulating layer. This substrate is referred to as an evaluation substrate A.
(4) Desmear treatment The evaluation substrate A is immersed in a swelling dip secu-ligand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 5 minutes at 60 ° C. and then used as a roughening solution. Soaked in Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, washed with water, and finally neutralized as a reduction of Atotech Japan Co., Ltd. It was immersed in Sholeucine securigant P at 40 ° C. for 5 minutes.
(5) Plating formation After desmearing, the laminate was immersed in an electroless copper plating solution containing PdCl ₂ . Then, it annealed by heating at 150 degreeC for 30 minutes, and it immersed in the copper sulfate electroplating liquid, and formed the plating conductor layer with the thickness of 30 micrometers. Finally, annealing was performed at 180 ° C. for 60 minutes.
(6) Sample adjustment A resist rape cut out in a circle (manufactured by Nitto Denko Corporation, ELEP masking tape N380) was attached on the plated conductor layer and immersed in an aqueous ferric chloride solution for 30 minutes. The portion of the plating conductor layer where the resist rape was not applied was removed, and an evaluation substrate was produced in which a circular plating conductor layer was formed on the insulating layer. Thereafter, a portion of the insulating layer was shaved to expose the underlying copper foil. And the exposed copper foil and the circular plating conductor layer were connected by wiring (wire). A DC power supply (TP018-3D, manufactured by Takasago Seisakusho Co., Ltd.) was connected to the wiring of the evaluation board, and a voltage of 3.3 V was applied for 200 hours at 130 ° C. and 85% RH. The resistance value was measured after 200 hours, and the resistance value of 1.0 × 10 ⁷ Ω or more was evaluated as “◯”, and the resistance value of less than 1.0 × 10 ⁷ Ω was determined as “×”. A thin film whose thickness accuracy was low and could not be measured was designated as “−”.

<Evaluation of surface smoothness and embedding>
(1) Observation of surface smoothness The evaluation substrate A was measured with a non-contact type surface roughness meter (WYKO NT3300 manufactured by Beeco Instruments, Inc.) on the insulating layer surface. The case where it exceeded was made into "x".
(2) Observation of embeddability The evaluation substrate A is observed with a micro microscope on the surface of the insulating layer, and “○” indicates that the substrate is firmly embedded without voids, and “×” indicates that voids are generated or resin is exuded. "

<Measurement of etching amount per unit area>
For varnishes A to G, uniformly apply with a die coater on a PET film coated with an alkyd release agent (hereinafter referred to as release PET) so that the thickness of the resin composition layer after drying is 10 μm. The cured product was obtained by heating at 180 ° C. for 30 minutes. Thereafter, the release PET was peeled off and dried at 130 ° C. for 15 minutes, and the mass immediately after the drying (initial mass (X1)), and after the drying, further desmear treatment and water washing were performed, and immediately after drying at 130 ° C. for 15 minutes. The mass (mass after desmear (X2)) was measured, and the etching amount of each cured product was determined by the following formula. The “desmear process” here is the same process as the above-described desmear process.

  Etching amount per unit area (g / m2) = (X1-X2) / surface area of cured product

<Measurement of elastic modulus>
For varnishes A to G, a cured product is obtained by applying uniformly with a die coater so that the thickness of the resin composition layer after drying is 40 μm on release PET and heating at 180 ° C. for 30 minutes. It was. The cured product was cut into a test piece having a width of 7 mm and a length of 40 mm, and dynamic mechanical analysis was performed in a tensile mode using a dynamic mechanical analyzer DMS-6100 (manufactured by Seiko Instruments Inc.). After mounting the test piece on the apparatus, measurement was performed under the measurement conditions of a frequency of 1 Hz and a heating rate of 5 ° C / min. The storage elastic modulus (E ′) value at 25 ° C. in this measurement was read.

<Measurement of minimum melt viscosity>
The melt viscosities of the second resin composition layers prepared in Examples 1 to 5 and Comparative Examples 1 to 7 were measured. Using a model Rheosol-G3000 manufactured by UBM Co., Ltd., using a parallel plate having a resin amount of 1 g and a diameter of 18 mm, a starting temperature of 60 ° C. to 200 ° C., a heating rate of 5 ° C./min, The minimum melt viscosity (poise) was measured under the measurement conditions of a measurement temperature interval of 2.5 ° C., vibration of 1 Hz, and strain of 1 deg.

<Thickness measurement>
The first layer and the second layer used in Examples and Comparative Examples were measured using a contact-type layer thickness meter (manufactured by Mitutoyo Corporation, MCD-25MJ).

(Production Example 1)
21 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation), 21 parts biphenyl type epoxy resin (epoxy equivalent 269, "NC3000L" manufactured by Nippon Kayaku Co., Ltd.), 5 parts of naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4700” manufactured by DIC Corporation), phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation), MEK having a solid content of 30% by mass and 1: 1 of cyclohexanone 120 parts of a solution) and 30 parts of a phenoxy resin (“YX1256” manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 40%) were heated and dissolved in a mixed solvent of 25 parts of MEK and 25 parts of cyclohexanone with stirring. There, 20 parts of triazine-containing phenol novolac resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass), naphthol-based curing agent (hydroxyl equivalent 215, manufactured by Tohto Kasei Co., Ltd.) SN-485 ", MEK solution with a solid content of 60%, 20 parts, curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd.," 2E4MZ "), 0.1 part, spherical silica (average particle size 0.5 μm, AD Co., Ltd.) 80 parts of Matex “SOC2”, polyvinyl butyral resin (“KS-1” manufactured by Sekisui Chemical Co., Ltd., a solution having a solid content of 15% dissolved in a mixed solvent having a mass ratio of ethanol and toluene of 1: 1) 40 Parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin composition varnish A.

(Production Example 2)
10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation) and liquid cyclohexanedimethanol type epoxy resin (epoxy equivalent 135, Nippon Steel Chemical Co., Ltd. ZX-1658) 4 Parts, 25 parts of biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.), 10 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4700” manufactured by DIC Corporation) , 10 parts of phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass) are dissolved in a mixed solvent of 25 parts of MEK and 25 parts of cyclohexanone with stirring. It was. There, 16 parts of a triazine-containing phenol novolak resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass), naphthol-based curing agent (hydroxyl equivalent 215, Nippon Steel Chemical Co., Ltd.) “SN-485” manufactured by MEK solution having a solid content of 60% 16 parts, curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2E4MZ”) 0.1 part, spherical silica (average particle size 1 μm, with aminosilane treatment ( 320 parts of Admatechs Co., Ltd. “SOC4” and 10 parts of a reactive flame retardant (hydroxyl equivalent: 162, “HCA-HQ” manufactured by Sanko Co., Ltd., 9.5% phosphorus content) are mixed in a high-speed rotating mixer. The resin composition varnish B was produced by uniformly dispersing.

(Production Example 3)
28 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Di-Mitsubishi Chemical Corporation) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4700” manufactured by Dainippon Ink & Chemicals, Inc.) ) 28 parts, 20 parts of phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass) were dissolved in 15 parts of MEK and 15 parts of cyclohexanone with stirring. . There, 27 parts of a triazine-containing phenol novolac resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass), naphthol-based curing agent (hydroxyl equivalent 215, Nippon Steel Chemical Co., Ltd.) “SN-485” manufactured by MEK solution having a solid content of 60% by weight 27 parts, curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2E4MZ”) 0.1 part, spherical silica (average particle size 0.5 μm, aminosilane) 70 parts treated ("SOC2" manufactured by Admatechs Co., Ltd.), 6 parts reactive flame retardant (hydroxyl equivalent: 162, "HCA-HQ" manufactured by Sanko Co., Ltd., phosphorus content: 9.5%), polyvinyl butyral resin ( 30 parts of “KS-1” manufactured by Sekisui Chemical Co., Ltd. and a 1: 1 solution of ethanol and toluene with a solid content of 15% by weight are mixed and dispersed uniformly with a high-speed rotary mixer. To produce a C.

(Production Example 4)
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation), 35 parts biphenyl type epoxy resin (epoxy equivalent 269, "NC3000L" manufactured by Nippon Kayaku Co., Ltd.), 8 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4700” manufactured by Dainippon Ink & Chemicals, Inc.), 15 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 30% solid content MEK solution) Were dissolved in 20 parts of MEK and 20 parts of cyclohexanone with stirring. There, 10 parts of a triazine-containing phenol novolac resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass), an active ester curing agent (hydroxyl group equivalent 223, manufactured by DIC Corporation “ "HPC-8000-65T", toluene solution with a solid content of 65% by mass), curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., "2E4MZ") 0.1 part, spherical silica (average particle size 0.5 μm, aminosilane) 300 parts of "SOC2" manufactured by Admatechs Corporation with treatment and 6 parts of reactive flame retardant (hydroxyl equivalent: 162, "HCA-HQ" manufactured by Sanko Co., Ltd., phosphorus content: 9.5%) are mixed. The resin composition varnish D was produced by uniformly dispersing with a rotary mixer.

(Production Example 5)
10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation), 10 parts biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.), 5 parts of a naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4700” manufactured by DIC Corporation) was dissolved in a mixed solvent of 10 parts of MEK and 10 parts of cyclohexanone with stirring. There, 11 parts of a triazine-containing phenol novolac resin (hydroxyl group equivalent 125, “LA7054 manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass), naphthol-based curing agent (hydroxyl group equivalent 215, manufactured by Tohto Kasei Co., Ltd.” SN-485 ", MEK solution having a solid content of 60%, 11 parts, curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd.," 2E4MZ "), 0.05 parts, spherical silica (average particle size 0.5 μm, AD Co., Ltd.) 20 parts of Matex “SOC2”, polyvinyl butyral resin (“KS-1” manufactured by Sekisui Chemical Co., Ltd., a solution having a solid content of 15% dissolved in a mixed solvent having a mass ratio of ethanol and toluene of 1: 1) 800 Parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin composition varnish E.

(Production Example 6)
0.1 part of a curing catalyst (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2E4MZ”), 320 parts of spherical silica (average particle size 0.5 μm, “SOC4” manufactured by Admatechs Co., Ltd. with aminosilane treatment) of Production Example 2 Resin composition varnish F was produced in the same manner as in Production Example 2 except that the ingredients were not blended.

(Production Example 7)
40 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4700” manufactured by Dainippon Ink and Chemicals, Inc.) Eight parts and 15 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, MEK solution with a solid content of 30%) were dissolved in 20 parts of MEK and 20 parts of cyclohexanone with stirring. There, 30 parts of triazine-containing phenol novolak resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass), spherical silica (average particle size 0.5 μm, manufactured by Admatechs Corporation) "SOC2") 300 parts, reactive flame retardant (hydroxyl equivalent 162, "HCA-HQ" manufactured by Sanko Co., Ltd., phosphorus content 9.5%) 6 parts, epoxy-modified polybutadiene (manufactured by Daicel Chemical Industries, Ltd.) 20 parts of “PB-3600”) were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin composition varnish G.

Example 1
<Preparation of the first layer>
The resin composition varnish A is uniformly applied with a die coater so that the thickness of the resin composition layer after drying is 2 μm on the release PET, and dried at 160 ° C. for 10 minutes, thereby releasing the mold. A first layer was obtained on PET.
<Preparation of the second layer>
The resin composition varnish B is uniformly applied with a die coater on the release PET so that the thickness of the resin composition layer after drying is 25 μm, and the resin composition varnish B is heated from 80 ° C. to 120 ° C. (average 100 ° C.). The 2nd layer was obtained on mold release PET by drying for minutes.
<Lamination of first layer and second layer>
Insulate by bonding at 90 ° C. for 15 seconds with vacuum laminating (batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.) so that the first layer and the second layer are in contact with each other. A resin sheet was produced.

(Example 2)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer of Example 1 was 8 μm.

(Example 3)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer of Example 1 was 5 μm and the resin composition varnish C was used for the second layer.

Example 4
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer of Example 1 was 5 μm and the resin composition varnish D was used for the second layer.

(Example 5)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer of Example 1 was 5 μm, the resin composition varnish D was used for the second layer, and the thickness was 100 μm. .

(Comparative Example 1)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer in Example 1 was 1 μm.

(Comparative Example 2)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer in Example 1 was 20 μm.

(Comparative Example 3)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer of Example 1 was 5 μm, the thickness was 5 μm using the resin composition varnish C for the second layer. .

(Comparative Example 4)
An insulating resin sheet was produced in the same manner as in Example 1 except that the resin composition varnish E was used for the first layer of Example 1 and the resin composition varnish C was used for the second layer.

(Comparative Example 5)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer of Example 1 was 5 μm and the drying condition of the second layer was 150 ° C. for 10 minutes.

(Comparative Example 6)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer of Example 1 was 5 μm and the resin composition varnish F was used for the second layer.

(Comparative Example 7)
An insulating resin sheet was produced in the same manner as in Example 1 except that the thickness of the first layer of Example 1 was 5 μm and the resin composition varnish G was used for the second layer.

  The results are shown in Table 1.

 As is clear from the results in Table 1, the insulating resin sheets of Examples 1 to 5 have excellent characteristics. On the other hand, in Comparative Example 1, since the thickness of the first layer was 1 μm, the surface smoothness was inferior. In Comparative Example 2, since the thickness of the first layer was 20 μm, it was difficult to adjust the laser processability of the first layer and the second layer, and the via shape became distorted. In Comparative Example 3, the second layer was thin and the surface smoothness and embeddability were poor. In Comparative Example 4, the elastic modulus of the first layer was low and the surface smoothness was inferior. In Comparative Example 5, the minimum melt viscosity of the second layer was large, the surface smoothness was inferior, and the embedding property was inferior, for example, voids were generated. In Comparative Example 6, since the minimum melt viscosity of the second layer is small and the thickness accuracy after lamination is low, the thin film insulation reliability cannot be evaluated, the surface smoothness is inferior, and the resin oozes out. The embeddability was also poor. In Comparative Example 7, the via shape became distorted because the etching amount of the second layer was too small.

 In the present invention, an insulating resin sheet excellent in via shape, thin film insulation reliability, surface smoothness and embedding property can be provided. Furthermore, a multilayer printed wiring board and a semiconductor device using the same can be provided. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.

Claims (16)

A support;
A first layer containing an epoxy resin, a curing agent and an inorganic filler formed on the support, wherein the elastic modulus of the first layer is 0.5 GPa or more, and the thickness of the first layer is A first layer that is 2-18 μm;
A second layer containing an epoxy resin, a curing agent, and an inorganic filler formed on the first layer, wherein the minimum melt viscosity of the second layer is 100 to 19,500 poise, and the thickness of the second layer Having a second layer of 10 to 120 μm,
The etching amount (E1) per unit area of the first layer and the etching amount (E2) per unit area of the second layer are expressed by E1 / E2 = 0.3-3. Resin sheet.  The insulating resin sheet according to claim 1, wherein the elastic modulus of the first layer is 0.5 GPa or more and 10 GPa or less.  The insulating resin sheet according to claim 1 or 2, wherein the first layer has a thickness of 2 to 8 µm.  The epoxy resin in the first layer contains at least one selected from a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a naphthylene ether type epoxy resin. The insulating resin sheet according to any one of the above.  The insulating resin sheet according to any one of claims 1 to 4, wherein an average particle size of the inorganic filler in the first layer is 0.01 to 0.8 µm.  The insulating resin sheet according to claim 1, wherein the second layer has a minimum melt viscosity of 100 to 5000 poise.  The insulating resin sheet according to claim 1, wherein the second layer has a thickness of 15 to 100 μm.  The insulation according to any one of claims 1 to 7, wherein when the resin component in the second layer is 100% by mass, the liquid epoxy resin in the second layer is 1 to 35% by mass. Resin sheet.  The insulating resin sheet according to any one of claims 1 to 8, wherein the inorganic filler in the second layer is surface-treated with a surface treatment agent.  The total thickness of said 1st layer and said 2nd layer is 15-120 micrometers, The insulating resin sheet of any one of Claims 1-9 characterized by the above-mentioned.  The insulating resin sheet according to claim 1, wherein the first layer and the second layer are made of different materials.  The etching amount (E1) per unit area of the first layer and the etching amount (E2) per unit area of the second layer are E1 / E2 = 0.5-2. The insulating resin sheet of any one of -11.  It is an insulating resin sheet for buildup layers of a multilayer printed wiring board, The insulating resin sheet of any one of Claims 1-12 characterized by the above-mentioned. (A) a step of laminating the insulating resin sheet according to any one of claims 1 to 13 on one side or both sides of an inner layer circuit board;
(B) a step of thermosetting the insulating resin sheet to form an insulating layer;
(C) a step of peeling the support,
(D) forming a blind via by drilling an insulating layer;
(E) a step of roughening the surface of the insulating layer;
(F) a step of plating the surface of the insulating layer after the roughening treatment to form a conductor layer;
A method for producing a multilayer printed wiring board containing
In the step of forming a blind via by drilling the insulating layer (D), the laser energy is 1 to 6 mJ,
(E) In the step of roughening the surface of the insulating layer, a roughening treatment with an oxidizing agent at 60 to 80 ° C. for 10 to 30 minutes is performed.  (E) In the step of roughening the surface of the insulating layer, a swelling treatment is performed at 50 to 80 ° C. for 5 to 20 minutes, followed by a water washing treatment, followed by a roughening treatment with an oxidizing agent. The manufacturing method of the multilayer printed wiring board of Claim 14.  A semiconductor device using a multilayer printed wiring board manufactured by the method according to claim 14.