KR20140005783A - Insulating resin sheet - Google Patents

Abstract

Provided is a heat insulation resin sheet which improves a via phenomenon, thin film insulation reliability, surface smoothness, and embeddability. The present invention is completed by controlling the etching amount of a first layer and a second layer in relation to the heat insulation resin sheet which includes a support layer, a first specific layer, and a second specific layer.

Description

Insulation resin sheet {INSULATING RESIN SHEET}

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

In recent years, miniaturization and high performance of electronic devices are progressing. In order to improve the mounting density of an electronic component, multilayer printed wiring boards are progressing in miniaturization and miniaturization of conductor wiring. Among these, as a manufacturing method of a multilayer printed wiring board, the buildup system which piles up a circuit-formed conductor layer and an insulating layer (interlayer insulation layer) alternately is used widely, and it is usual for formation of the fine conductor wiring in the said buildup system. The additive method is adopted, and the semi-additive method is particularly mainstream.

On the other hand, in patent document 1, it is described that multilayering a resin composition layer and giving each layer a different function, but it was difficult to stabilize quality, such as mixing each layer. In patent document 2, although the insulated resin sheet which has a hardened | cured material layer and an contact bonding layer is disclosed, it does not mention at all about the via shape of a punching process.

Japanese Re-publication Publication No. 2008-90835 Japanese Unexamined Patent Publication No. 2010-28036

MEANS TO SOLVE THE PROBLEM The present inventors made various examinations in order to improve the performance of the multilayered film, and produced the multilayer printed wiring board. As a result, in the multilayered film, the energy adjustment is at the time of laser processing by the difference of the property of each layer. It is difficult and a new problem arises that a step | step arises in the via of each layer, and the via shape is crushed. Therefore, the present inventors have diligently studied and 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 an object of the present invention is to provide an insulating resin sheet excellent in via shape, thin film insulation reliability, surface smoothness and embedding properties.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, in the insulated resin sheet which has a support layer, the specific 1st layer formed on the said support body, and the specific 2nd layer formed on the said 1st layer, a 1st layer and By controlling the etching amount of the second layer, the present invention has been completed.

The present invention includes the following contents.

[1] A first layer containing a support and 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 2 to 18 µm. A second layer containing one layer and 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 from 100 to 19500 poise, and the thickness of the second layer is from 10 to 120 μm. It has a 2nd layer which is a phosphorus, and etching amount E1 per unit area of a said 1st layer, and etching amount E2 per unit area of a said 2nd layer are represented by E1 / E2 = 0.3-3, Insulation resin sheet characterized by the above-mentioned. .

[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 thickness of the said 1st layer is 2-8 micrometers, The insulated resin sheet as described in [1] or [2] characterized by the above-mentioned.

[4] The epoxy resin in the first layer contains at least one member selected from naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and naphthylene ether type epoxy resin [1] to The insulated resin sheet in any one of [3].

[5] The insulating resin sheet according to any one of [1] to [4], wherein the 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 minimum melt viscosity of the second layer is 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] 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, wherein the insulation according to any one of [1] to [7] Resin sheet.

[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 treating agent.

[10] The insulating resin sheet according to any one of [1] to [9], wherein the total thickness of the first layer and the second layer is 15 to 120 µm.

[11] The insulated resin sheet according to any one of [1] to [10], wherein the first layer and the second layer are made of different materials.

[12] Any of [1] to [11], wherein 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 to 2. The insulated resin sheet of any one of Claims.

[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 or both surfaces of the inner layer circuit board, and (B) thermosetting the insulating resin sheet to form an insulating layer. Process, (C) process of peeling support body, (D) process of punching through insulating layer to form blind via, (E) process of roughening the surface of insulation layer, (F) plating on surface of insulation layer after roughening process A method of manufacturing a multilayer printed wiring board comprising a step of forming a conductor layer, wherein the step of forming a blind via by punching through the insulating layer (D) comprises laser energy of 1 to 6 mJ, and the (E) insulation. In the process of roughening a layer surface, the roughening process by the oxidizing agent for 10 to 30 minutes is performed at 60-80 degreeC, The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned.

[15] In the step of roughening the surface of the (E) insulating layer, performing a swelling treatment for 5 to 20 minutes at 50 to 80 ° C, followed by washing with water, and then performing a roughening treatment with an oxidizing agent. The manufacturing method of the multilayer printed wiring board as described in [14] characterized by the above-mentioned.

[16] A semiconductor device comprising a multilayer printed wiring board manufactured by the method described in [14] or [15].

In the insulating resin sheet which has a support body, the specific 1st layer formed on the said support body, and the specific 2nd layer formed on the said 1st layer, via shape and thin film insulation are controlled by controlling the etching amount of a 1st layer and a 2nd layer. It was possible to provide an insulating resin sheet excellent in reliability, surface smoothness and embedding properties.

[Insulation resin sheet]

The insulated resin sheet of this invention is a 1st layer containing a support body and the epoxy resin, hardening | curing agent, and inorganic filler formed on the said support body, The elasticity modulus of a said 1st layer is 0.5 GPa or more, and the thickness of the said 1st layer is 2 to A second layer containing a first layer having a thickness of 18 μm and 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 19500 poise, and the thickness of the second layer Has a second layer having a thickness of 10 to 120 μm, and controls the etching amount E1 per unit area of the first layer and the etching amount E2 per unit area of the second layer to E1 / E2 = 0.3 to 3 It is done. In addition, on the exposed surface side of the second layer, a protective film may be provided to prevent adhesion of dust or the like.

In the insulating resin sheet of the present invention, the surface smoothness and the via shape are improved by defining the elastic modulus and the thickness of the first layer, and the embedding properties and the surface smoothness can be improved by defining the minimum melt viscosity and the thickness of the second layer. Can be. Then, by controlling the etching amount E1 per unit area of the first layer and the etching amount E2 per unit area of the second layer to E1 / E2 = 0.3 to 3, the first layer and the second layer generated after the desmear It is possible to suppress the step difference of the vias and to improve the via shape. Here, etching amount is an index of the rough state of the hardened | cured material with respect to a desmear process, and it controls an etching amount to E1 / E2 = 0.3-3, Preferably it is 0.5-2, and, at the time of desmear process, The difference in the rough state of a 2nd layer can be reduced, and it can be set as a favorable via shape. For this reason, it is excellent in the interlayer conduction reliability of a multilayer printed wiring board, and is suitable as an insulating resin sheet for the insulating layer of a multilayer printed wiring board. Moreover, it can use more suitably as the insulated resin sheet for buildup layers of a multilayer printed wiring board, and the insulated resin sheet for forming a conductor layer by plating.

[Support]

As a support body of this invention, a plastic film and a metal foil are mentioned. Specifically, as the plastic film, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyester such as polyethylene naphthalate, polycarbonate, acryl, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone And polyimide. Among these, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and a cheap polyethylene terephthalate film is especially preferable. Copper foil, aluminum foil, etc. are mentioned as metal foil. In terms of versatility, a plastic film is preferable, and in the case of using a plastic film, it is preferable to use a support on which the surface to be formed of the resin layer is released in order to improve peelability. As a mold release agent used for a mold release process, if a resin layer can peel from a support body, it will not specifically limit, For example, a silicone type mold release agent, an alkyd resin type mold release agent, a polyolefin resin, a urethane resin, a fluororesin etc. are mentioned. Moreover, you may use the commercially available plastic film with a release layer, As a preferable thing, it is SK-1, AL-5, AL-7 which is a PET film which has a release layer which has an alkyd resin type mold release agent as a main component, for example (Lintec Co., Ltd.) etc. are mentioned. In addition, the plastic film may apply the mat process and the corona treatment, and may form a release layer on the said process surface. In addition, although metal foil can be removed with an etching solution, you may use the said metal foil as a conductor layer, without removing. Although the thickness of a support body is not specifically limited, The range of 10-150 micrometers is preferable, and the range which is 25-50 micrometers is more preferable.

In the case of having a protective film, a plastic film such as a support can be used. Moreover, surface treatment, such as a mad process and a corona treatment, may be given to the protective film, and the above-mentioned mold release process may be applied. As for the thickness of a protective film, 3-30 micrometers is preferable.

[Resin composition]

The 1st layer and the 2nd layer of this invention are layered resin compositions. As a resin composition, if it contains (a) epoxy resin, (b) hardening | curing agent, and (c) inorganic filler, it can be used without a restriction | limiting in particular. Moreover, a thermoplastic resin, a hardening accelerator, and another component can also be mix | blended. Hereinafter, the compounding component 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 two or more epoxy groups 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 novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene Epoxy resin, naphthylene ether epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, anthracene epoxy resin, linear aliphatic epoxy resin, The epoxy resin which has a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring containing epoxy resin, a cyclohexane dimethanol type epoxy resin, a trimethylol type epoxy resin, a halogenated epoxy resin, etc. are mentioned. These may be used singly or in combination of two or more.

Among them, 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, and glycidyl ester from the viewpoint of thin film insulation reliability improvement. The epoxy resin which has a type epoxy resin, an anthracene type epoxy resin, and a butadiene structure is preferable. 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 resin in view of lowering the crosslinking density at the time of thermosetting the first layer and improving the top shape of the via. And one or more selected from naphthylene ether type epoxy resins. Specifically, for example, bisphenol A type epoxy resin ("Epicoat 828EL", "YL980" by Mitsubishi Chemical Co., Ltd.), bisphenol F type epoxy resin ("jER806H" by Mitsubishi Chemical Co., Ltd. product) , "YL983U"), naphthalene-type bifunctional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS" by DIC Corporation), naphthalene type | system | group tetrafunctional epoxy resin (DIC Corporation " HP4700 "," HP4710 "), naphthol type epoxy resin (" ESN-475V "by Shin-Nitetsu Chemical Co., Ltd.), epoxy resin (" PB-3600 "by Daicel Chemical Co., Ltd.) which has butadiene structure. ), An epoxy resin having a biphenyl structure (`` NC3000H '', `` NC3000L '', `` NC3100 '' manufactured by Nihon Kayaku Co., Ltd., `` YX4000 '', `` YX4000H '', `` YX4000HK '', manufactured by Mitsubishi Chemical Corporation), "YL6121"), anthracene type epoxy resin ("YX8800" by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin (DIC Corporation make) `` EXA-7310 '', `` EXA-7311 '', `` EXA-7311L '', `` EXA7311-G3 ''), glycidyl ester-type epoxy resin (`` EX711 '', `` EX711 '' of Nagase Chemtex Co., Ltd., ( Ltd.) "R540" manufactured by Printech Co., Ltd. may be mentioned.

The epoxy resin can improve the embedding property by containing a liquid epoxy resin. Moreover, it is preferable to use a liquid epoxy resin and a solid epoxy resin together. The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20 ° C. The solid epoxy resin has three or more epoxy groups in one molecule and an aromatic system in a solid state at a temperature of 20 ° C. Epoxy resins are preferred. The term "aromatic epoxy resin" in the present invention means an epoxy resin having an aromatic ring structure in its molecule. As an epoxy resin, when using a liquid epoxy resin and a solid epoxy resin together, since the balance of hardening physical properties of a resin composition is provided, the compounding ratio (liquid epoxy resin: solid epoxy resin) is 1: 0.1-1: by mass ratio. The range of 2 is preferable, the range of 1: 0.3-1: 1.8 is more preferable, The range of 1: 0.6-1: 1.5 is further more preferable.

As the liquid epoxy resin, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, glycidyl ester type epoxy resins, naphthalene type epoxy resins are preferable, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferred. Resin and a naphthalene type epoxy resin are more preferable. These may be used singly or in combination of two or more. As a solid epoxy resin, a tetrafunctional naphthalene type epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a biphenyl type epoxy resin, a naphthylene An ether type epoxy resin is preferable and a naphthol type epoxy resin and a biphenyl type epoxy resin are more preferable. These may be used singly or in combination of two or more.

In the resin composition of this invention, when the non volatile component in a resin composition is 100 mass% from a viewpoint of improving the thin film insulation reliability of the hardened | cured material of a resin composition, it is preferable that content of an epoxy resin is 3-40 mass%. It is more preferable that it is 5-35 mass%, and it is still more preferable that it is 10-30 mass%. In particular, from the viewpoint of improving the embedding of the second layer, when the resin component in the second layer is 100% by mass, the content of the liquid epoxy resin in the second layer is preferably 1 to 35% by mass, and is 3 to 30. Mass% is more preferable, and 6-25 mass% is more preferable.

(b) curing agent

Although it does not specifically limit as a hardening | curing agent used for this invention, A phenol type hardening | curing agent, an active ester type hardening | curing agent, a cyanate ester type hardening | curing agent, a benzoxazine type hardening | curing agent, an acid anhydride type hardening | curing agent, etc. are mentioned, A phenolic hardening | curing agent and an active ester type | system | group It is preferable to use 1 or more types chosen from a hardening | curing agent and a cyanate ester type hardening | curing agent. These may be used singly or in combination of two or more.

The phenol-based curing agent is not particularly limited, but a biphenyl-type curing agent, a naphthalene-type curing agent, a phenol novolak type curing agent, a naphthylene ether type curing agent and a triazine skeleton-containing phenol type curing agent are preferable. Specifically, MEH-7700, MEH-7810, MEH-7851 (made by Meiwa Kasei Co., Ltd.) of a biphenyl type hardening | curing agent, NHN, CBN, GPH (made by Nihon Kayaku Co., Ltd.) of a naphthalene type hardening | curing agent, SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Shin-Nitetsu Chemical Co., Ltd.), EXB9500 (manufactured by DIC Co., Ltd.), TD2090 (manufactured by DIC Co., Ltd.), And EXB-6000 (manufactured by DIC Corporation) of a naphthylene ether type curing agent. LA3018, LA7052, LA7054, LA1356 (made by DIC Corporation) etc. are mentioned as a specific example of a triazine skeleton containing phenolic hardening | curing agent. In particular, a naphthalene type hardening | curing agent and a triazine skeleton containing phenol type hardening | curing agent are more suitable.

Generally, the active ester curing agent includes compounds having two or more ester groups having high reaction activity in one molecule such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. It is preferably used. It is preferable that the said active ester type hardening | curing agent is obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound, a hydroxy compound, and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type 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. As the phenol compound or naphthol compound, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, trihydroxybenzo Phenone, tetrahydroxy benzophenone, fluoroglucin, benzene triol, dicyclopentadienyl diphenol, phenol novolak, etc. are mentioned. The active ester type hardener can use 1 type (s) or 2 or more types. Specifically, an active ester curing agent containing a dicyclopentadienyldiphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent which is an acetylate of phenol novolac, and an ester monohydrate of phenol novolac A system hardening | curing agent etc. are preferable, The active ester type hardening | curing agent containing a dicyclopentadienyl diphenol structure is more preferable at the point which can melt | dissolve the melt viscosity of a resin composition layer and can improve a landfill property among these. Commercially available products include dicyclopentadienyldiphenol structures, which are EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (DIC Co., Ltd., active group equivalent approximately 223), an active ester curing agent which is an acetylide of phenol novolac YLH1026 (Mitsubishi Chemical Co., Ltd., active group equivalent approximately 200), YLH1030 (Mitsubishi Chemical) And YLH1048 (manufactured by Mitsubishi Chemical Co., Ltd., about 245 equivalents of active group equivalent).

Examples of the cyanate ester curing agent include, but are not limited to, novolac (phenol novolac type, alkylphenol novolak type, etc.) cyanate ester type curing agent, dicyclopentadiene type cyanate ester type curing agent, bisphenol type Bisphenol F, bisphenol S, etc.) cyanate ester curing agents, and partially triarylated prepolymers thereof. The weight-average molecular weight of the cyanate ester-based curing agent is not particularly limited, but is preferably 500 to 4500, more preferably 600 to 3000. As a specific example of a cyanate ester type hardening | curing agent, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene- 1, 5- phenylene cyanate), 4,4'- methylene bis (2, 6-dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis ( 4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4 Polyfunctional cyanate resins derived from bifunctional cyanate resins such as -cyanatephenyl) thioether and bis (4-cyanatephenyl) ether, phenol novolac, cresol novolac, and dicyclopentadiene structure-containing phenol resins And tripolymers in which these cyanate resins are partially triazine, etc. These may be used alone or in combination of two or more thereof. As the cyanate ester resin that is commercially available, a part or all of the phenol novolak-type polyfunctional cyanate ester resin (Lonza Japan Co., Ltd. product, PT30, cyanate equivalent 124) and the bisphenol A dicyanate are triazineized. Prepolymers (manufactured by Lonza Japan Co., Ltd., BA230, cyanate equivalents 232), dicyclopentadiene structure-containing cyanate ester resins (Lonza Japan Co., Ltd. product, DT-4000, DT-7000) Can be mentioned.

When the compounding ratio of an epoxy resin and a hardening | curing agent makes the epoxy group number of an epoxy resin 1, the ratio which becomes the range of 0.3-2.0 of the number of reactors of a hardening | curing agent is preferable, and the ratio which becomes the range of 0.5-1.0 is more preferable. In addition, the epoxy group number of the epoxy resin which exists in a resin composition is the value which divided the solid content mass of each epoxy resin by the epoxy equivalent, and it totals it about all the epoxy resins, and the reactor number of a hardening | curing agent divided the solid content mass of each hardening | curing agent by the reactor equivalent. The value is the sum total of all the hardening | 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, titanium oxide, and the like, and silica and alumina are preferable, and amorphous silica and fused silica are particularly preferred. Silicas, such as crystalline silica, synthetic silica, hollow silica, and spherical silica, are preferable, and spherical silica and fused silica are more preferable. These may be used alone or in combination of two or more. From a viewpoint of the improvement of the filling property to a resin composition, spherical fused silica is more preferable. Examples of commercially available spherical fused silica include "SOC2" and "SOC1" manufactured by ADMATEX.

The average particle diameter 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 improving surface smoothness. Do. On the other hand, the average particle diameter of the inorganic filler is preferably 0.01 µm or more, more preferably 0.05 µm or more, and even more 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 a 1st layer, 0.01-0.8 micrometer is preferable and, as for the average particle diameter of the inorganic filler in a 1st layer, 0.01-0.6 micrometer is more preferable. The average particle diameter of an inorganic filler can be measured by the laser diffraction scattering method based on a fine scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured with a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is determined as the average particle diameter. The sample to be measured may preferably be an inorganic filler dispersed in water by ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba Sesaku Sho, etc. can be used.

Since content of an inorganic filler prevents the flexibility of a sheet form from falling, and lowers a linear thermal expansion rate, when the nonvolatile component in a resin composition is 100 mass%, 35-85 mass% is preferable, 40-75 mass% is more preferable.

The inorganic filler is surface-treated with surface treatment agents such as an epoxy silane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent to improve its moisture resistance. It is preferable to make it. These may be used singly or in combination of two or more. Among these, an aminosilane coupling agent is preferable because it is excellent in moisture resistance, dispersibility, hardened | cured material, etc. In particular, in order to improve the embedding of a 2nd layer, it is preferable that the inorganic filler in a 2nd layer is surface-treated with the surface treating agent. As a commercial item, "KBM403" (3-glycidoxy propyl trimethoxysilane) by Shin-Etsu Chemical Co., Ltd., "KBM803" (3- mercaptopropyl trimethoxysilane) by Shin-Etsu Chemical Co., Ltd. ), "KBE903" (3-aminopropyltriethoxysilane) by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) by Shin-Etsu Chemical Co., Ltd. ), "KBM103" (phenyl trimethoxysilane) by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) by Shin-Etsu Chemical Co., Ltd., etc. are mentioned.

(d) thermoplastic resin

Examples of the thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyethersulfone resins, polysulfone resins, and the like, and phenoxy resins and polyvinyl acetal resins include desirable. The thermoplastic resin may be used singly or in combination of two or more.

The weight average molecular weight of polystyrene conversion of a thermoplastic resin is preferable in the range of 8000-70000, The range of 10000-60000 is more preferable, The range of 20000-60000 is further more preferable. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of polystyrene conversion of the thermoplastic resin is Shodex K-800P manufactured by Showa Denko Co., Ltd. as a column using LC-9A / RID-6A manufactured by Shimadzu Corporation / K-804L / K-804L can be measured using a chloroform or the like as a mobile phase at a column temperature of 40 ° C and calculated using a calibration curve of standard polystyrene.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used singly or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" manufactured by Mitsubishi Chemical Corporation. And bisphenol acetphenone skeleton-containing phenoxy resins; in addition, "FX280" and "FX293" manufactured by Totogsei Co., Ltd., "YL7553", "YL6794" by Mitsubishi Chemical Co., Ltd., "YL7213", "YL7290", "YL7482", etc. are mentioned.

As a specific example of polyvinyl acetal resin, Denka Butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd. Esrek BH series manufactured by Denki Chemical Co., Ltd. make , BX series, KS series, BL series, BM series and the like.

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

(e) curing accelerators

As a hardening accelerator, an organic phosphine compound, an imidazole compound, an amine adduct compound, a tertiary amine compound, etc. are mentioned, for example. When content of a hardening accelerator makes 100 mass% the sum total of the non volatile component of an epoxy resin and a hardening | curing agent, it is preferable to use in 0.01-3 mass%. A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

The flame retardant, rubber particle, organic solvent, other additives, etc. can be mix | blended suitably with the resin composition of this invention.

The resin composition of this invention mixes the said components suitably, Furthermore, if necessary, it is mixed by kneading means, such as three rolls, a ball mill, a bead mill, a sand mill, or stirring means, such as a super mixer and a planetary mixer. By kneading or mixing, it can manufacture as a resin varnish.

[First Layer]

The 1st layer of this invention can be produced as a resin composition layer which formed the resin composition layer on the support body. A resin composition layer can prepare the resin composition containing an organic solvent, apply | coat the said resin composition on a support body, and can form a resin composition layer by drying and heating, for example. As drying and heating conditions, 5 to 30 minutes are preferable at 130-170 degreeC, and 5 to 20 minutes are more preferable at the point of adjustment of an elasticity modulus and the productivity improvement of a board | 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 do not mix, and the excellent insulating resin sheet can be manufactured. In particular, from the viewpoint of improving the surface smoothness, 0.8 GPa or more is preferable, 1 GPa or more is more preferable, 1.5 GPa or more is more preferable, and 2 GPa or more is further more preferable. In addition, there is no restriction | limiting in particular in an upper limit, Usually, they are 10 GPa or less and 5 GPa or less.

The thickness of the first layer of the present invention is controlled to be 2 to 18 mu m. By doing in this way, the insulating resin sheet which is excellent in surface smoothness and also excellent in via shape can be manufactured. From the point of surface smoothness improvement, 3 micrometers or more are more preferable, and 4 micrometers or more are more preferable. 16 micrometers or less are preferable, 14 micrometers or less are more preferable, 12 micrometers or less are more preferable, 10 micrometers or less are still more preferable, and 8 micrometers or less are especially preferable at the point which makes a via shape favorable.

[Second layer]

The 2nd layer of this invention can also be produced as a resin composition layer which layered the resin composition on the support body using the above resin composition. A resin composition layer can prepare the resin composition containing an organic solvent, apply | coat the said resin composition on a support body, and can form a resin composition layer by drying, for example. As dry conditions, 3 to 15 minutes are preferable at 80-120 degreeC. As a resin composition, it is preferable to adjust so that a 1st layer and a 2nd layer may be comprised from different materials, Specifically, the resin composition from which the kind of compounding component differs, and the resin composition from which content of a compounding component differs are mentioned. By doing in this way, the characteristic performance can be provided to each of a 1st layer and a 2nd layer.

The lowest 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 the embedding property and surface smoothness can be manufactured. In order to prevent air from entering together at the time of embedding, 18000 poise or less is preferable, 15000 poise or less is more preferable, 10000 poise or less is still more preferable, 8000 poise or less is still more preferable, 5000 poise or less is especially preferable. From the point of preventing bleeding at the time of embedding, 200 poise or more is preferable, 400 poise or more is more preferable, 600 poise or more is more preferable, 800 or more is further more preferable.

The thickness of the second layer of the present invention is controlled to be 10 to 120 mu m. By doing in this way, the insulated resin sheet excellent in surface smoothness and embedding property can be manufactured, and it becomes the thing excellent also in thinning. 15 micrometers or more are preferable at the point of the surface smoothness improvement or the embedding improvement. 100 micrometers or less are preferable, 50 micrometers or less are more preferable, and 25 micrometers or less are more preferable at the point which makes a via shape favorable.

[Production Method of Insulation Resin Sheet]

Various methods can be used as a manufacturing method of an insulated resin sheet. For example, the resin composition layer which is a 1st layer is formed on a support body, a resin composition is apply | coated on it, and the resin composition layer which is a 2nd layer can be formed by drying. Moreover, after producing what formed the resin composition layer which is a 1st layer on a support body, and what formed the resin composition layer which is a 2nd layer on another support body, respectively, the method of bonding each resin composition layer surface by lamination is also mentioned. As for the conditions at the time of bonding by lamination, lamination temperature 70-110 degreeC, lamination time 5-30 second, and lamination pressure 1-10 kgf / cm <2> are preferable.

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, further preferably 20 to 40 µm.

[Multilayer printed wiring board using insulation resin sheet]

Hereinafter, an example of the manufacturing method of the multilayer printed wiring board using the insulated resin sheet of this invention is described in detail.

In the manufacturing method of the multilayer printed wiring board of this invention, the process of (A) laminating | stacking an insulating resin sheet on one side or both sides of an inner layer circuit board, (B) the process of thermosetting an insulating resin sheet, and forming an insulating layer, (C ) Process of peeling support body, (D) process of perforating to insulation layer to form blind via, (E) process of roughening surface of insulation layer, (F) plating to surface of insulation layer after roughening process, conductor layer Forming step, and the like.

(A) In the process 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 laid on the inner side circuit board side and laminated on one side or both sides of the inner layer circuit board. . The inner layer circuit board herein has a conductor layer patterned (circuit formed) on one or both surfaces of a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. When manufacturing a multilayer printed wiring board, it refers to the intermediate product in which the insulating layer and the conductor layer should be further formed. In addition, it is preferable that the surface of the conductor layer is subjected to a roughening treatment in advance by a blackening treatment or the like from the viewpoint of improving the adhesion between the insulating layer and the inner circuit board.

In the step (A), when the insulating resin sheet has a protective film, after removing the protective film, the insulating resin sheet and the inner layer circuit board are preheated as necessary, and the inner layer circuit is pressed and heated while pressing the insulating resin sheet. Compress the substrate. In the insulated resin sheet of this invention, the method of laminating | stacking to a circuit board under reduced pressure by the vacuum lamination method is used suitably. The conditions of the laminate are not particularly limited, but for example, the crimping temperature (laminate temperature) is preferably 70 to 140 ° C, and the crimping pressure (laminate pressure) is preferably 1 to 11 kgf / cm 2 (9.8 × 10 ^4). To 107.9 × 10 ⁴ N / m 2), and the compression time (lamination time) is preferably 5 to 180 seconds, and is preferably laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. In addition, the laminating method may be a batch type or a continuous type by a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. As a commercial vacuum laminator, for example, the vacuum applicator of Nichigo Morton Co., Ltd., a vacuum press type laminator of Meiki Sesaku Sho, Ltd., a roll type dry coater of Hitachi Industries, Ltd., Hitachi AIC Co., Ltd. ) Vacuum laminator and the like.

In the step (B) of thermosetting the insulating resin sheet to form an insulating layer, the insulating resin sheet is laminated on the inner circuit board, and then the first layer and the second layer are thermally cured, thereby forming the inner layer circuit board. An insulating layer (hardened material) can be formed on it. What is necessary is just to select conditions of thermosetting suitably according to the kind, content, etc. of the resin component in a resin composition, Preferably it is 20 to 180 minutes at 150 degreeC-220 degreeC, More preferably, it is 30 to 120 minutes at 160 degreeC-210 degreeC Is selected from the range of. Moreover, by thermosetting without peeling a support body, foreign matter adhesion, such as dust and dust, during thermosetting can be prevented.

(C) In a process of peeling a support body ((C) process), a support body is peeled off. When a base material is a plastic film, peeling of a base material can be performed by mechanically removing by a manual or automatic peeling apparatus. In addition, when a base material is metal foil, metal foil can be melt | dissolved by etching liquid etc., and metal foil can be peeled and removed.

In the step (D) of forming the blind via by punching the insulating layer (step (D)), the blind via is formed by punching the insulating layer. Although the drilling process can be performed by well-known methods, such as a drill, a laser, and a plasma, for example, combining these methods as needed, drilling by a laser, such as a carbon dioxide laser and a YAG laser, is preferable. In view of versatility, 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 blind vias with a carbon dioxide laser, the number of shots is usually selected between 1 and 5 shots, although the number of shots also varies depending on the depth of the blind vias to be formed and the hole diameter. In order to speed up the processing of the blind via and to improve the productivity of the multilayer printed wiring board, the shorter number is better, and the shorter number is preferably 1 to 3. In the case of processing with a plurality of shots, the cycle mode, which is a plurality of shots having a time interval, is preferable because the burst mode, which is a continuous shot, is filled with processing heat in the hole, and the via shape tends to be crushed.

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 a high energy, the short pulse has a better via processing shape.

In the case of punching by a carbon dioxide laser, in the insulating resin sheet of the present invention, in order to suppress the step difference between the first layer and the second layer and to improve the via shape, it is preferable to adjust the laser energy to 1 to 6 mJ. It is preferable and it is more preferable to adjust to 2-5mJ.

(E) In the process of roughening the insulating layer surface ((E) process), after peeling a support body, a roughening process of the insulating layer surface is carried out. In the case of dry roughening treatment, plasma treatment may be mentioned. In the case of wet roughening treatment, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid may be mentioned in this order. have. The wet roughening process is preferable in that the smear in the blind via can be removed while forming the uneven anchor on the surface of the insulating layer.

The swelling treatment by the swelling liquid is performed by immersing the insulating layer in the swelling liquid for 5 to 20 minutes (preferably 8 to 15 minutes at 55 to 70 ° C) at 50 to 80 ° C. Examples of the swelling liquid include an alkali solution, a surfactant solution, and the like, and preferably an alkaline solution. Examples of the alkali 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 P) manufactured by Atotech Japan Co., Ltd., and Swelling Dip Securiganth SBU (Swelling Dip Securiganth SBU). Etc. can be mentioned. In addition, the via shape can be better maintained by performing a swelling treatment, followed by washing with water, and then roughening with an oxidizing agent.

The roughening treatment by the oxidizing agent is performed by immersing the insulating layer in the oxidizing agent solution for 10 to 30 minutes (preferably 15 to 25 minutes at 70 to 80 ° C) at 60 to 80 ° C. Examples of the oxidizing agent include alkaline permanganate solutions in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid. In addition, the concentration of the permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as Atotech Japan Co., Ltd. product condensate compact CP and dosing solution security P, are mentioned, for example.

Neutralization treatment by neutralizing liquid is performed by immersing in neutralizing liquid for 3 to 10 minutes (preferably 3 to 8 minutes at 35-45 degreeC) at 30-50 degreeC. As a neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial item, Atotech Japan Co., Ltd. product reduction solucin securant P is mentioned.

In the insulated resin sheet of this invention, the 1st which generate | occur | produces after desmear by controlling the etching amount E1 per unit area of a 1st layer and the etching amount E2 per unit area of a 2nd layer to E1 / E2 = 0.3-3. It is possible to suppress the step difference between the vias of the layer and the second layer, and to improve the via shape. In particular, by adopting the above roughening treatment conditions, the via shape can be more easily controlled.

(F) In the process of forming a conductor layer by plating on the insulating layer surface after roughening process ((F process)), a conductor layer can be formed in the insulating layer surface. As a method of plating formation, forming a conductor layer on an insulating layer by dry plating or wet plating is mentioned. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. As wet plating, the method of forming a conductor layer by combining electroless plating and electrolytic plating after a roughening process, the method of forming a plating resist of the opposite pattern to a conductor layer, and the method of forming a conductor layer only by electroless plating, etc. are mentioned. have. As a method of pattern formation after that, the subtractive method, the semiadditive method, etc. which are known to a person skilled in the art can be used, for example.

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

<Semiconductor Device>

The semiconductor device can be manufactured by using the multilayered printed circuit board manufactured by the method of the present invention. The semiconductor device can be manufactured by mounting the semiconductor chip in the conductive portion of the multilayered printed circuit board of the present invention. The &quot; conduction site &quot; is a &quot; location for transmitting electrical signals in the multilayered printed circuit board &quot;, and may be a surface or a buried site. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting a semiconductor chip in 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 method, a flip chip mounting method, a bumpless buildup layer ( BBUL), the mounting method by anisotropic conductive film (ACF), the mounting method by non-conductive film (NCF), etc. are mentioned.

[ Example ]

Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, "part" in the following description means a "mass part."

First, the measurement method and evaluation method in the physical property evaluation in the present specification will be described.

<Evaluation of the empty shape>

(1) Substrate treatment of substrate

Both surfaces of the glass cloth base epoxy resin double-sided copper clad laminate [18 micrometers of copper foil, substrate thickness 0.3mm, R5715ES by Matsushita Denko Co., Ltd.] are immersed in Merck Co., Ltd. CZ8100, and the roughening process of a copper surface is performed. It was.

(2) Lamination of Insulation Resin Sheet

The insulated resin sheet produced in the Example and the comparative example was laminated so that a 2nd layer might contact both surfaces of a copper clad laminated board using batch type vacuum pressurizer laminator MVLP-500 (made by Meiki Co., Ltd. brand name). Lamination was performed by depressurizing for 30 second, making atmospheric pressure 13 hPa or less, and crimping at 100 degreeC and pressure 0.74 Mpa for 30 second after that.

(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 hardening, the support body was peeled off and the blind via was formed from the 1st layer using the laser processing machine (CO2 laser apparatus: ML605GTWII-P by Mitsubishi Denki Co., Ltd.). The conditions of laser irradiation were performed by pulse width 13 microseconds, energy 3mJ, the number of shots one shot, and the mask diameter 1.1mm.

(5) Dismigration processing

After blind via formation, it was immersed for 5 minutes at 60 degreeC in swelling dip security P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. which is a swelling liquid, and, as a roughening liquid, Atotech Japan Reduction of Atotech Japan Co., Ltd. as a neutralizing solution after immersion at 80 ° C for 20 minutes in a condensate compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) and washing with water. It was immersed in solleucine securitag P at 40 degreeC for 5 minutes. Then, it dried for 15 minutes at 130 degreeC. This removed the smear in a blind via.

(6) observation of vias

Cross sections of the vias were observed by SEM. The wall level | step difference of the 1st layer and the 2nd layer is 5 micrometers or more, and it is set as "x", and the wall level | step difference is less than 5 micrometers, but the via diameter became large, "(triangle | delta)" and the wall surface level | step difference are less than 5 micrometers, and enlargement of a via diameter is carried out. What was set as "(circle)" was made.

<Evaluation of Thin Film Insulation Reliability>

(1) Substrate treatment of substrate

Both sides of glass cloth base material epoxy resin double-sided copper clad laminated board (18 micrometers of copper foil, 60% of residual ratios, substrate thickness 0.3mm, R5715ES by Matsushita Denko Co., Ltd.) which formed inner layer circuit were made into Merck ( Note) It was immersed in CZ8100 of manufacture, and the roughening process of the copper surface was performed.

(2) Lamination of Insulation Resin Sheet

The insulated resin sheet produced in the Example and the comparative example was laminated so that a 2nd layer might contact both surfaces of the copper clad laminated board using the batch type vacuum pressurizer laminator MVLP-500 (made by Meiki Corporation). Lamination was performed by depressurizing for 30 second, making atmospheric pressure 13 hPa or less, and crimping at 100 degreeC and pressure 0.74 Mpa for 30 second after that.

(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 evaluation substrate A.

(4) desmear

Evaluation board | substrate A was immersed in the swelling dip security P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. which is swelling liquid at 60 degreeC for 5 minutes, and then Atotech Japan as a roughening liquid Reduction of Atotech Japan Co., Ltd. as a neutralizing solution after immersion at 80 ° C for 20 minutes in a condensate compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) and washing with water. It was immersed in solleucine securitag P at 40 degreeC for 5 minutes.

(5) plating formation

After the desmear, the laminate was immersed in an electroless copper plating solution containing PdCl ₂ . Then, it annealed by heating at 150 degreeC for 30 minutes, it immersed in the copper sulfate electrolytic plating liquid, and the plating conductor layer was formed in the thickness of 30 micrometers. Finally, annealing was performed at 180 degreeC for 60 minutes.

(6) sample adjustment

A resist strip (Nittto Denko Co., Ltd. Eleb Masking Tape N380) cut out in a circular shape was attached to the plated conductor layer and immersed in an aqueous ferric chloride solution for 30 minutes. The evaluation board | substrate with which the circular plating conductor layer was formed on the insulating layer was removed by removing the plating conductor layer of the part to which the resist label was not affixed. 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 Corporation Co., Ltd.) was connected to the wiring of the evaluation board, and a voltage of 3.3 V was given for 200 hours at a temperature of 85% RH at 130 ° C. The resistance value was measured after 200 hours, the thing of resistance value being 1.0 * 10 <^7> ohm or more was made into "(circle)", and the thing less than 1.0 * 10 <^7> Ω was made into "x". It was set as "-" that the thickness precision of the thin film was low and could not be measured.

<Evaluation of surface smoothness and landfill>

(1) Observation of Surface Smoothness

The evaluation board | substrate A was measured by the non-contact surface roughness machine (WYKO NT3300 by a non-coiled instrument) by measuring the surface of an insulating layer, and when the wave | wire is 2 micrometers or less, it is set as "(circle)" and the case exceeding 2 micrometers is made into "x". It was.

(2) Observation of landfill

The evaluation board | substrate A observed the surface of the insulating layer with the microscopic microscope, and it was made into "(circle)" that what was buried reliably without a void, and made into "x" that void generation and resin leaked out.

<Measurement of etching amount per unit area>

Regarding varnishes A to G, on a PET film coated with an alkyd-based release agent (hereinafter referred to as release PET), the coating composition was uniformly applied with a die coater so that the thickness of the resin composition layer after drying was 10 μm, and heated at 180 ° C. for 30 minutes. The hardened | cured material was obtained by this. Thereafter, the release PET was peeled off, dried at 130 ° C. for 15 minutes, the mass immediately after the drying (initial mass (X1)), followed by further desmearing and washing with water, followed by drying at 130 ° C. for 15 minutes. The mass (post-smear mass (X2)) immediately after making it was measured, and the etching amount of each hardened | cured material was calculated | required by the following formula. In addition, the "desmear process" here is the same process as the said desmear process.

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

<Measurement of elastic modulus>

Regarding varnishes A to G, a cured product was obtained by uniformly applying a die coater on a mold release PET so that the thickness of the resin composition layer after drying became 40 μm and heating at 180 ° C. for 30 minutes. The hardened | cured material was cut into the test piece of width 7mm and length 40mm, and dynamic mechanical analysis was performed in tension mode using the dynamic mechanical analysis apparatus DMS-6100 (made by Seiko Instruments Co., Ltd.). After mounting a test piece to the said apparatus, it measured on the measurement conditions of the frequency of 1 Hz and a temperature increase rate of 5 degree-C / min. The value of the storage elastic modulus (E ') at 25 degreeC in such a measurement was read.

<Measurement of minimum melt viscosity>

Melt viscosity of the resin composition layer of the 2nd layer created in Examples 1-5 and Comparative Examples 1-7 was measured. Using a model Rheosol-G3000 manufactured by U.B.M Co., Ltd., the resin amount is 1 g and a parallel plate having a diameter of 18 mm, and the temperature increase rate is 5 ° C./min from the start temperature of 60 ° C. to 200 ° C. The lowest melt viscosity was measured under measurement conditions of a temperature interval of 2.5 ° C., a vibration of 1 Hz, and a deformation of 1 deg.

<Measurement of thickness>

The 1st layer and the 2nd layer used by the Example and the comparative example were measured using the contact type layer thickness gauge (the Mitsutoyo Corporation make, MCD-25MJ).

(Production Example 1)

21 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, `` Epicoat 828EL '' of Mitsubishi Chemical Co., Ltd.) and biphenyl type epoxy resin (Epoxy equivalent 269, "NC3000L" of Nippon Kayaku Co., Ltd. product) ) 21 parts, naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 163, `` HP4700 '' of DIC Corporation) and phenoxy resin (`` YX6954BH30 '' of Mitsubishi Chemical Co., Ltd., solid 30 mass%) 120 parts of MEK and cyclohexanone) and 30 parts of phenoxy resin ("YX1256" manufactured by Mitsubishi Chemical Co., Ltd., 40% of solid content 40%) of MEK 25 parts and 25 parts of cyclohexanone It melt | dissolved by stirring in a mixed solvent. There, 20 parts of triazine containing phenol novolak resins (hydroxyl equivalent 125, "LA7054" of DIC Corporation, MEK solution of 60 mass% of solid content), naphthol type hardening | curing agent (hydroxyl equivalent 215, Totogasei Co., Ltd.) "SN-485" of manufacture, 20 parts of MEK solutions of 60% of solid content), 0.1 part of hardening catalysts ("2E4MZ" by Shikoku Chemical Co., Ltd.), and spherical silica (average particle diameter: 0.5 micrometer, ADD) 80 parts of `` SOC2 '' made by Matex, polyvinyl butyral resin ("KS-1" made by Sekisui Chemical Co., Ltd.), 15% of the solid content dissolved in the mixed solvent whose mass ratio of ethanol and toluene is 1: 1. Solution) 40 parts were mixed, and it disperse | distributed uniformly by the high speed rotary mixer, and the resin composition varnish A was produced.

(Production Example 2)

10 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, `` Epicoat 828EL '' of Mitsubishi Chemical Co., Ltd.) and liquid cyclohexane dimethanol type epoxy resin (Epoxy equivalent 135, Shinnitetsukaka-ku) ZX-1658) 4 parts, biphenyl type epoxy resin (269 epoxy equivalent, "NC3000L" of Nihon Kayaku Co., Ltd.), and naphthalene type tetrafunctional epoxy resin (Epoxy equivalent 163, DIC Corporation) 10 parts of "HP4700" of manufacture, 10 parts of phenoxy resin ("YX6954BH30" of Mitsubishi Chemical Corporation, 1: 1 solution of 30 mass% of solid content MEK and cyclohexanone) MEK 25 parts and cyclohexane It heated and melted in 25 parts of mixed solvents, stirring. There, 16 parts of triazine containing phenol novolak resins (hydroxyl equivalent 125, DIC Corporation "LA7054", MEK solution of 60 mass% of solid content), naphthol type hardening | curing agent (hydroxyl equivalent 215, Shinnitetsukaka Ward (note 16 parts of "SN-485", 60% of solid content MEK solution), a hardening catalyst (made by Shikoku Chemical Co., Ltd., "2E4MZ"), spherical silica (average particle diameter 1 micrometer, aminosilane-treated) Mix 320 parts of `` SOC4 '' manufactured by Admatex Co., Ltd., 10 parts of reactive flame retardant (162 equivalents of hydroxyl group, `` HCA-HQ '' manufactured by Sanco Co., Ltd., phosphorus content of 9.5%) and uniformly by high speed rotary mixer. It disperse | distributed so that the resin composition varnish B was produced.

(Production Example 3)

28 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, `` Epicoat 828EL '' of Mitsubishi Chemical Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (Epoxy equivalent 163, Dainippon Ink Chemical Co., Ltd. product) 28 parts of "HP4700", 20 parts of phenoxy resin ("YX6954BH30" of Mitsubishi Chemical Co., Ltd., 1: 1 solution of MEK and cyclohexanone of 30 mass% of solid content) MEK 15 parts, cyclohexanone 15 It melt | dissolved by stirring, stirring in a part. There, 27 parts of triazine-containing phenol novolak resins (hydroxyl equivalent 125, DIC Corporation make "LA7054", MEK solution of 60 mass% of solid content), naphthol type hardening | curing agent (hydroxyl equivalent 215, Shinnitetsu Chemical Co., Ltd. ( 27 parts of "SN-485" of the manufacture), MEK solution of 60 weight% of solid content), 0.1 part of hardening catalysts (made by Shikoku Chemical Co., Ltd., "2E4MZ"), spherical silica (average particle diameter: 0.5 micrometer, amino) 70 parts of `` SOC2 '' manufactured by Admatex Co., Ltd., reactive flame retardant (hydroxyl equivalent 162, `` HCA-HQ '' manufactured by Sanco Co., Ltd., phosphorus content 9.5%) 6 parts, polyvinyl butyral 30 parts of resin ("KS-1" of Sekisui Chemical Co., Ltd., 1: 1 solution of ethanol and toluene of 15 weight% of solid content) are mixed, and it disperse | distributes uniformly with a high speed rotary mixer, and the resin composition varnish C is prepared. Produced.

(Production Example 4)

15 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, `` Epicoat 828EL '' of Mitsubishi Chemical Co., Ltd.) and biphenyl type epoxy resin (Epoxy equivalent 269, "NC3000L" of Nippon Kayaku Co., Ltd. product) ) 35 parts, naphthalene-type tetrafunctional epoxy resin (Epoxy equivalent 163, Dainippon Ink & Chemicals Co., Ltd. product "HP4700") 8 parts, phenoxy resin ("YX7553BH30" of Mitsubishi Chemical Co., Ltd.) 15 parts of MEK solution of 30% of solid content was melt | dissolved by stirring, while stirring 20 parts of MEK and 20 parts of cyclohexanone. There, 10 parts of triazine containing phenol novolak resins (hydroxyl equivalent 125, "LA7054" of DIC Corporation make, MEK solution of 60 mass% of solid content), active ester type hardening | curing agent (hydroxyl equivalent 223, DIC Co., Ltd. product) "HPC-8000-65T", 60 parts of toluene solution of 65 mass% of solid content, 0.1 part of hardening catalysts (made by Shikoku Chemical Co., Ltd., "2E4MZ"), spherical silica (0.5 micrometer in average particle diameter, aminosilane) A high-speed rotary mixer is mixed with 300 parts of treated SOC2 manufactured by ADMATEX, 6 parts of reactive flame retardant (162 equivalents of hydroxyl equivalent, HCA-HQ manufactured by Sanco, 9.5% phosphorus). It disperse | distributed uniformly and the resin composition varnish D was produced.

(Production Example 5)

10 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, `` Epicoat 828EL '' of Mitsubishi Chemical Co., Ltd.) and biphenyl type epoxy resin (Epoxy equivalent 269, "NC3000L" of Nippon Kayaku Co., Ltd. product) 10 parts and 5 parts of naphthalene type | mold tetrafunctional epoxy resins (epoxy equivalent 163, "HP4700" by DIC Corporation) were melt | dissolved by stirring in 10 parts of MEK and 10 parts of cyclohexanone, stirring. There, 11 parts of triazine-containing phenol novolak resins (hydroxyl equivalent 125, "LA7054" of DIC Corporation, MEK solution of 60 mass% of solid content), naphthol type hardening | curing agent (hydroxyl equivalent 215, Totogasei Co., Ltd.) 11 parts of "SN-485" of manufacture, MEK solution of 60% of solid content), 0.05 parts of hardening catalysts ("2E4MZ" by Shikoku Chemical Co., Ltd.), and spherical silica (average particle diameter: 0.5 micrometer, Inc.) 20 parts of `` SOC2 '' manufactured by Matex, polyvinyl butyral resin (KS-1 manufactured by Sekisui Chemical Co., Ltd.), 15% solids dissolved in a mixed solvent having a mass ratio of ethanol and toluene 1: 1. Solution) 800 parts were mixed, and it disperse | distributed uniformly with the high speed rotary mixer, and the resin composition varnish E was produced.

(Production Example 6)

0.1 part of curing catalyst (manufactured by Shikoku Chemical Co., Ltd., "2E4MZ") of Production Example 2, 320 parts of spherical silica (average particle diameter: 0.5 µm, aminosilane-treated "SOC4") A resin composition varnish F was produced in the same manner as in Production Example 2 except that there was no blend.

(Production Example 7)

40 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, `` Epicoat 828EL '' of Mitsubishi Chemical Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (Epoxy equivalent 163, Dainippon Ink Chemical Co., Ltd. product) 8 parts of "HP4700" and 15 parts of phenoxy resins ("YX7553BH30" of Mitsubishi Chemical Co., Ltd., MEK solution of 30% of solid content) were melt | dissolved by stirring, stirring 20 parts of MEK and 20 parts of cyclohexanone. There, 30 parts of triazine containing phenol novolak resins (hydroxyl equivalent 125, "LA7054" of DIC Corporation, MEK solution of 60 mass% of solid content), spherical silica (0.5 micrometer of average particle diameters, Adma Co., Ltd.) 300 parts of `` SOC2 '' made by tex, reactive flame retardant (hydroxyl equivalent 162, `` HCA-HQ '' made by Sanko Co., Ltd., phosphorus content 9.5%) 6 parts, epoxy modified polybutadiene (Deisel Chemical Co., Ltd.) 20 parts of "PB-3600" of manufacture were mixed, it was disperse | distributed uniformly by the high speed rotary mixer, and the resin composition varnish G was produced.

(Example 1)

<Production of the first layer>

The resin composition varnish A was apply | coated uniformly with a die coater on a mold release PET so that the thickness of the resin composition layer after drying might be set to 2 micrometers, and it dried at 160 degreeC for 10 minutes, and obtained the 1st layer on mold release PET.

<Production of the second layer>

On the mold release PET, the resin composition varnish B was uniformly applied on the mold release PET with a die coater so that the thickness of the resin composition layer after drying became 25 μm, and dried for 6 minutes from 80 ° C. to 120 ° C. (average 100 ° C.). A second layer was obtained.

<Bonding of 1st layer and 2nd layer>

Insulating resin sheet was produced by making a 1st layer and a 2nd layer contact, and bonding together at 90 degreeC and 15 second with a vacuum lamination (batch-type vacuum pressurization laminator MVLP-500 (MEIKISE Corporation Corporation brand name)). It was.

(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)

The insulating resin sheet was produced by the method similar to Example 1 except having set the thickness of the 1st layer of Example 1 to 5 micrometers, and using the resin composition varnish C for the 2nd layer.

(Example 4)

The insulating resin sheet was produced by the method similar to Example 1 except having set the thickness of the 1st layer of Example 1 to 5 micrometers, and using the resin composition varnish D for the 2nd layer.

(Example 5)

The insulating resin sheet was produced by the method similar to Example 1 except having made thickness of the 1st layer of Example 1 into 5 micrometers, using resin composition varnish D for the 2nd layer, and making thickness into 100 micrometers.

(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)

The insulating resin sheet was produced by the method similar to Example 1 except having set the thickness of the 1st layer of Example 1 to 5 micrometers, using resin composition varnish C for the 2nd layer, and making thickness into 5 micrometers.

(Comparative Example 4)

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

(Comparative Example 5)

The insulating resin sheet was produced by the method similar to Example 1 except having set the thickness of the 1st layer of Example 1 to 5 micrometers, and making the drying conditions of a 2nd layer into 150 degreeC and 10 minutes.

(Comparative Example 6)

The insulating resin sheet was produced by the method similar to Example 1 except having set the thickness of the 1st layer of Example 1 to 5 micrometers, and using the resin composition varnish F for the 2nd layer.

(Comparative Example 7)

The insulating resin sheet was produced by the method similar to Example 1 except having set the thickness of the 1st layer of Example 1 to 5 micrometers, and using resin composition varnish G for the 2nd layer.

The results are shown in Table 1.

As apparent from the results of Table 1, the insulating resin sheets of Examples 1 to 5 exhibited excellent characteristics. On the other hand, in the comparative example 1, since the thickness of the 1st layer was 1 micrometer, surface smoothness fell. In the comparative example 2, since the thickness of a 1st layer was 20 micrometers, adjustment of the laser workability of a 1st layer and a 2nd layer was difficult, and the via shape was crushed. In Comparative Example 3, the second layer was thin, resulting in poor surface smoothness and embedding. In the comparative example 4, the elasticity modulus of the 1st layer was low and surface smoothness fell. In the comparative example 5, the minimum melt viscosity of the 2nd layer was large, surface smoothness fell, and voids generate | occur | produced, and also the embedding property was inferior. In the comparative example 6, since the minimum melt viscosity of the 2nd layer was small and the thickness precision after lamination was low, evaluation of thin film insulation reliability was not possible, surface smoothness fell, resin leaked out, and also the embedding property was also inferior. In Comparative Example 7, since the etching amount of the second layer was too small, the via shape was crushed.

In the present invention, it is possible to provide an insulating resin sheet excellent in via shape, thin film insulation reliability, surface smoothness and embedding properties. Moreover, the multilayer printed wiring board and semiconductor device using the same can be provided. In addition, electric products such as computers, cellular phones, digital cameras, and televisions mounted thereon, and vehicles such as motorcycles, automobiles, trams, ships, and aircrafts can be provided.

Claims (16)

With a support,
A first layer containing an epoxy resin, a curing agent, and an inorganic filler formed on the support, wherein the first layer has an elastic modulus of 0.5 GPa or more and a thickness of the first layer of 2 to 18 µm;
A second layer containing an epoxy resin, a curing agent, and an inorganic filler formed on the first layer, wherein the lowest melt viscosity of the second layer is from 100 to 19500 poise, and the thickness of the second layer is from 10 to 120 μm Have 2 layers,
The etching amount (E1) per unit area of the said 1st layer and the etching amount (E2) per unit area of a said 2nd layer are represented by E1 / E2 = 0.3-3, The insulation resin sheet characterized by the above-mentioned. The elasticity modulus of a said 1st layer is 0.5 GPa or more and 10 GPa or less, The insulated resin sheet of Claim 1 characterized by the above-mentioned. The thickness of the said 1st layer is 2-8 micrometers, The insulated resin sheet of Claim 1 characterized by the above-mentioned. 2. The insulation according to claim 1, wherein the epoxy resin in the first layer contains at least one selected from naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin and naphthylene ether type epoxy resin. Resin sheet. The insulated resin sheet of Claim 1 whose average particle diameter of the inorganic filler in a said 1st layer is 0.01-0.8 micrometer. The minimum melt viscosity of a said 2nd layer is 100-5000 poise, The insulated resin sheet of Claim 1 characterized by the above-mentioned. The thickness of the said 2nd layer is 15-100 micrometers, The insulated resin sheet of Claim 1 characterized by the above-mentioned. The insulating resin sheet according to claim 1, wherein the liquid epoxy resin in the second layer is 1 to 35% by mass when the resin component in the second layer is 100% by mass. The inorganic filler in a 2nd layer is surface-treated with the surface treating agent, The insulating resin sheet of Claim 1 characterized by the above-mentioned. The total thickness of the said 1st layer and said 2nd layer is 15-120 micrometers, The insulated resin sheet of Claim 1 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 insulating resin sheet according to claim 1, wherein 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 to 2. The insulating resin sheet according to any one of claims 1 to 12, which is an insulating resin sheet for a buildup layer of a multilayer printed wiring board. (A) The process of laminating | stacking the insulating resin sheet in any one of Claims 1-12 on one side or both sides of an inner layer circuit board,
(B) thermosetting the insulating resin sheet to form an insulating layer,
(C) peeling off the support;
(D) punching through the insulating layer to form blind vias,
(E) roughening the surface of the insulating layer,
(F) The manufacturing method of the multilayer printed wiring board containing the process of plating on the surface of the insulating layer after a roughening process, and forming a conductor layer,
In the step of forming a blind hole by drilling in the insulating layer (D), the laser energy is 1 to 6mJ,
In the process of roughening the said (E) insulating layer surface, the roughening process by the oxidizing agent for 10 to 30 minutes is performed at 60-80 degreeC, The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned. The process for roughening the surface of the (E) insulating layer according to claim 14, wherein the swelling treatment is performed at 50 to 80 ° C. for 5 to 20 minutes, followed by washing with water, followed by roughening treatment with an oxidizing agent. The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned. The semiconductor device manufactured using the multilayer printed wiring board manufactured by the method of Claim 14.