KR20140005782A - Resin sheet attached with support - Google Patents

Abstract

Provided is a resin sheet with a support, which has excellent smear clearance and coating strength in spite of low dielectric loss tangent and linear thermal expansion coefficients. The present invention is completed by using the resin sheet which includes a support, a first specific layer formed on the support, and a second specific layer formed on the first specific layer.

Description

Resin sheet with supporter {RESIN SHEET ATTACHED WITH SUPPORT}

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

In recent years, miniaturization and high performance of electronic devices have progressed, and in a semiconductor package board | substrate, a buildup layer was multilayered, and wiring refinement | miniaturization and high density were calculated | required.

Various measures were taken about this. For example, Patent Document 1 discloses a resin composition containing an epoxy resin and an active ester resin. It is described that the insulating layer formed by such a composition can achieve both dielectric properties and heat resistance. However, the performance was not necessarily satisfactory.

Japanese Laid-Open Patent Publication No. 2009-235165

In the resin composition, in order to obtain a cured product having excellent dielectric properties, many active ester compounds are blended, and in order to lower the thermal expansion rate, many inorganic fillers are preferably blended. In this case, in the via formation by a carbon dioxide laser, The problem that the laser workability and smear removal property tends to deteriorate is newly discovered. On the other hand, when the active ester compound is reduced, the smear removal property is improved, but it has been confirmed that there is a problem that the plating peel strength tends to decrease with respect to the copper plating formed after the desmear due to the increase in the dielectric tangent.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object to be solved by the present invention is to provide a resin sheet with a support having excellent smear removability and plating peel strength despite low dielectric loss tangent and linear thermal expansion coefficient.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, by using a resin sheet with a support body 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, The present invention has been completed.

That is, the present invention includes the following contents.

[1] A first layer containing an epoxy resin, an active ester compound, and an inorganic filler formed on a support and the support, wherein when the nonvolatile component in the first layer is 100% by mass, the active ester compound is 5% by mass. Active ester compound when the non-volatile component in the second layer is 100% by mass as a second layer containing a first layer that is at least% and an epoxy resin, an active ester compound, and an inorganic filler formed on the first layer. It has this 2nd layer which is 5 mass% or less, The resin sheet with a support body characterized by the above-mentioned.

(2) The average particle diameter of the said inorganic filler is 0.01-3 micrometers, The resin sheet with a support body as described in said [1] characterized by the above-mentioned.

[3] The resin sheet with a support according to [1] or [2], wherein the content of the inorganic filler is 40 to 90 mass%.

[4] The resin sheet with a support according to any one of [1] to [3], wherein the inorganic filler is surface treated with a surface treating agent.

[5] The resin sheet with a support according to [4], wherein the carbon amount per unit surface area of the inorganic filler is 0.02 to 1 mg / m 2.

[6] The resin sheet with a support according to any one of [1] to [5], wherein the thickness of the second layer is 2 µm or more.

[7] The resin sheet with a support according to any one of [1] to [6], wherein the resin sheet is thermally cured to form an insulating layer, and the thermal expansion coefficient of the insulating layer is 25 ppm or less.

[8] The resin sheet is thermally cured to form an insulating layer, and the dielectric loss tangent (measuring frequency of 5.8 GHz) of the insulating layer is 0.0065 or less, with the support according to any one of [1] to [7]. Resin sheet.

[9] The arithmetic mean roughness Ra is 150 nm or less, and the root mean square roughness Rq is 220 nm or less after heat curing the resin sheet to form an insulating layer and roughening the surface of the insulating layer. The resin sheet with a support body in any one of [1]-[8].

[10] The peel strength of the conductor layer and the insulating layer obtained by thermosetting the resin sheet to form an insulating layer, roughening the surface of the insulating layer and plating, and the insulating layer is at least 0.5 kgf / cm [1] The resin sheet with a support body in any one of [9].

[11] The resin sheet with a support according to any one of [1] to [10], which is a resin sheet with a support for an insulating layer of a multilayer printed wiring board.

[12] The resin sheet with a support according to any one of [1] to [11], which is a resin sheet with a support for a buildup layer of a multilayer printed wiring board.

[13] (A) A step of laminating the resin sheet with a support according to any one of [1] to [12] on one or both surfaces of the inner layer circuit board; (B) The resin sheet with the support is thermally cured to form an insulating layer. Forming process, (C) Forming a via hole by drilling into insulating layer, (D) Peeling support body, (E) Process of roughening insulation layer surface, (F) Insulation layer surface after roughening process A method for manufacturing a multilayer printed wiring board comprising a step of plating a conductive layer to form a conductor layer, wherein the top diameter (diameter) of the via hole of the insulating layer It is 65 micrometers or less, The manufacturing method of the multilayer printed wiring board.

[14] A semiconductor device using a multilayer printed wiring board manufactured by the method described in [13].

By using the resin sheet with a support 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, although a dielectric loss tangent and a coefficient of linear thermal expansion are low, smear It was possible to provide a resin sheet with a support having excellent removability and plating peel strength.

[Resin Sheet with Support]

The resin sheet with a support of this invention is a 1st layer containing a support and an epoxy resin, an active ester compound, and an inorganic filler formed on the said support, and when the non-volatile component in the said 1st layer is 100 mass%, it is active. When the non-volatile component in the said 2nd layer is 100 mass% as a 2nd layer containing the 1st layer whose ester compound is 5 mass% or more, and the epoxy resin, active ester compound, and inorganic filler formed on the said 1st layer. And an active ester compound having a second layer of 5% by mass or less. 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 resin sheet with a support body of this invention, when the non volatile component in a 1st layer is 100 mass%, when an active ester compound is 5 mass% or more, dielectric loss tangent can be made low and plating peeling strength can be made favorable. . And when the non volatile component in a 2nd layer is 100 mass%, when an active ester compound is 5 mass% or less, a coefficient of thermal expansion can be made low and the smear removal property in carbon dioxide laser processing can be made favorable. For this reason, it is excellent in the interlayer conduction reliability of a multilayer printed wiring board, and is suitable as a resin sheet with a support body for insulating layers of a multilayer printed wiring board. Moreover, it can use more suitably as a resin sheet with a support body for buildup layers of a multilayer printed wiring board, and a resin sheet with a support body 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, acrylic, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone, Polyimide, and the like. 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. From the point of versatility, a plastic film is preferable, and when using a plastic film, it is preferable to use the support body by which the surface which contact | connected the 1st layer in the mold release process was used in order to improve peelability. As a mold release agent used for a mold release process, if a 1st 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, a plastic film may add a mat process and a corona treatment, and may form a release layer on the said process surface. In addition, metal foil may be removed by an etching solution, and you may use the said metal foil as a conductor layer, without removing it. 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 resin sheets which layered the resin composition. As a resin composition, if an epoxy resin, an active ester compound, and an inorganic filler are included, 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, from the viewpoint of improving heat resistance, 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 Resin, anthracene type epoxy resin, and the epoxy resin which has butadiene structure are preferable. 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. ), Epoxy resin having a biphenyl structure ("NC3000H", "NC3000L", "NC3000L", "NC3100" manufactured by Nippon Kayaku Co., Ltd., "YX4000", "YX4000H", "YX4000HK", manufactured by Mitsubishi Chemical Co., Ltd., "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.

An epoxy resin can improve the handleability of a resin sheet 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. In addition, the aromatic epoxy resin in this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. As an epoxy resin, when using a liquid epoxy resin and a solid epoxy resin together, since the balance of hardened | cured material property 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. And naphthalene type epoxy resins are more preferable. These may be used singly or in combination of two or more. Examples of the solid epoxy resin 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. A 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.

When content of an epoxy resin reduces the linear thermal expansion coefficient of the hardened | cured material of a resin sheet, when making the nonvolatile component in a 1st layer 100 mass%, it is preferable that it is 3-40 mass%, It is 5-30 mass It is more preferable that it is%, and it is still more preferable that it is 7-20 mass%. The same range is preferable for a 2nd layer.

(b) active ester compounds

The active ester compound used for this invention is a compound which has 1 or more active ester group in 1 molecule. The active ester compound can react with an epoxy resin or the like, and a compound having two or more active ester groups in one molecule is preferable. Generally, the compound which has 2 or more of ester groups with high reaction activity in 1 molecule, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, is used preferably. .

From the viewpoint of heat resistance improvement, an active ester compound obtained from a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is more preferable. And the active ester compound obtained from what made 1 type (s) or 2 or more types selected from a carboxylic compound, a phenol compound, a naphthol compound, and a thiol compound react is more preferable. And the aromatic compound which has two or more active ester group in 1 molecule obtained from what made the carboxylic acid compound and the aromatic compound which has a phenolic hydroxyl group react is further more preferable. And an aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group, and an aromatic compound having two or more active ester groups in one molecule of the aromatic compound. Particularly preferred. Moreover, it may be linear or multibranched. If the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if the compound has an aromatic ring, the heat resistance can be increased.

Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Of these, suicinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable. Specific examples of the thiocarboxylic acid compound include thioacetic acid, thiobenzoic acid, and the like.

Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxy benzophenone, tetrahydroxy benzophenone, fluoroglucin, benzene triol, dicyclopentadienyl diphenol, phenol novolac and the like. Among these, from the viewpoint of heat resistance improvement and solubility improvement, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, benzenetriol, dicyclopenta Dienyldiphenol and phenol novolac are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxy Benzophenone, tetrahydroxy benzophenone, fluoroglucin, benzene triol, dicyclopentadienyl diphenol, and phenol novolak are more preferable, and 1, 5- dihydroxy naphthalene, 1, 6- dihydroxy naphthalene , 2,6-dihydro More preferred are hydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolak, and 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyldiphenol, and phenol novolak are further preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6 Dihydroxynaphthalene and dicyclopentadienyldiphenol are particularly preferred, and dicyclopentadienyldiphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol, triazinedithiol and the like. An active ester compound may use together 1 type (s) or 2 or more types.

Specifically, an active ester compound containing a dicyclopentadienyldiphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylate of phenol novolac, and an benzoylate of phenol novolak An ester compound is preferable, and the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadienyl diphenol structure are more preferable among these. As a commercial item, it is an active ester compound containing a dicyclopentadienyl diphenol structure, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (made by DIC Corporation), and an active ester compound containing a naphthalene structure EXB9416-70BK ( DC808 (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylide of phenol novolac, and YLH1026 (Mitsubishi Chemical ( Note) manufacture) etc. are mentioned.

The content of the active ester compound contained in the first layer lowers the dielectric tangent, improves the plated peel strength, and can exhibit sufficient peel strength even when thermally cured by adhesion of the support. When the foot component is 100 mass%, it is 5 mass% or more. Preferably it is 5-30 mass%, More preferably, it is 5-25 mass%, More preferably, it is 5-20 mass%. On the other hand, content of the active ester compound contained in a 2nd layer makes a non-volatile component in a 2nd layer 100 mass% from a viewpoint of making a linear coefficient of thermal expansion low, and improving the smear removal property in carbon dioxide laser processing. In that case, it will be 5 mass% or less. Preferably it is 0-5 mass%, More preferably, it is 0.5-5 mass%, More preferably, it is 1-4 mass%.

Moreover, when (a) the number of epoxy groups of an epoxy resin is 1, since the mechanical property of hardened | cured material is improved, (b) the number of reactors of an active ester compound is preferably 0.2 to 2, more preferably 0.3 to 1.5, , 0.4 to 1 is more preferable. Here, "the number of epoxy groups of an epoxy resin" is the value which totaled the value obtained by dividing the solid content mass of each epoxy resin which exists in a resin composition by the epoxy equivalent, regarding all the epoxy resins. In addition, "reactor" means the functional group which can react with an epoxy group, and "reactor number" is the value which totaled the value which divided all the value which divided the solid content mass of the active ester compound which exists in a resin composition by the reactor equivalent.

(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. From a viewpoint of the improvement of the filling property to a resin sheet, spherical fused silica is more preferable. These may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SOC2" and "SOC1" manufactured by Ado-Matex.

Although the average particle diameter of an inorganic filler is not specifically limited, 3 micrometers or less are preferable from a viewpoint of forming a micro wiring over an insulating layer, and the viewpoint of suppressing smear generation at the time of drilling by increasing the total surface area of an inorganic filler. 2 micrometers or less are more preferable, 1 micrometer or less is still more preferable, 0.8 micrometer or less is further more preferable, 0.6 micrometer or less is especially preferable. On the other hand, in the case where the resin composition is used as a varnish, from the viewpoint of preventing the viscosity of the varnish from rising and the handleability thereof from being lowered, 0.01 µm or more is preferable, 0.03 µm or more is more preferable, and 0.07 µm or more is more preferable. 0.1 micrometer or more is further more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie 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.

Although content of an inorganic filler is not specifically limited, From a viewpoint of preventing the flexibility of a sheet form from falling, when the non volatile component in a 1st layer is 100 mass%, 90 mass% or less is preferable, and 85 mass % Or less is more preferable, and 80 mass% or less is further more preferable. The same range is preferable for a 2nd layer. In addition, from the viewpoint of lowering the thermal expansion rate of the insulating layer and increasing the total surface area of the inorganic filler to suppress the generation of smears during drilling, and to facilitate the removal of smears during roughening, the nonvolatile components in the first layer. When it makes 100 mass%, 40 mass% or more is preferable, 50 mass% or more is more preferable, 60 mass% or more is more preferable, 65 mass% or more is further more preferable. The same range is preferable for a 2nd layer.

The inorganic filler is preferably surface-treated with a surface treatment agent for improving moisture resistance and dispersibility. As a surface treating agent, 1 or more types chosen from an epoxysilane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent are preferable. Among these, an aminosilane coupling agent is preferable because it is excellent in moisture resistance, dispersibility, hardened | cured material, etc. 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" (phenyltrimethoxysilane) by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethylsilazane) by Shin-Etsu Chemical Co., Ltd., etc. are mentioned.

In addition, the inorganic filler surface-treated with the surface treating agent can measure the amount of carbon per unit surface area of the inorganic filler after washing with a solvent (for example, methyl ethyl ketone). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After the supernatant is removed and the solids are dried, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Sesaku Sho, etc. can be used.

In view of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, 1 mg / m <2> or less is preferable, 0.8 mg / m <2> or less is more preferable, and 0.5 mg / m <2> or less is preferable at the point which prevents the raise of the melt viscosity of a resin varnish and the melt viscosity in a film form.

(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 gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the polystyrene conversion of a thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / manufactured by Showa Denko Co., Ltd. as a column. K-804L / K-804L can be measured at the column temperature of 40 degreeC using chloroform etc. as a mobile phase, and can be computed using the analytical curve of a standard polystyrene.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, Phenoxy resins having one or more skeletons selected from adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons are preferred. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. The phenoxy resin may be used singly or in combination of two or more. As a specific example of a phenoxy resin, Mitsubishi Chemical Co., Ltd. product "1256", "4250" (all bisphenol A skeleton containing phenoxy resin), "YX8100" (bisphenol S skeleton containing phenoxy resin), "YX6954" ( Bisphenol acetphenone skeleton-containing phenoxy resin), "YL7553" (fluorene skeleton-containing phenoxy resin), "FX280", "FX293" by Totogasei Co., Ltd., and "YL6794" by Mitsubishi Chemical Co., Ltd. , "YL7213", "YL7290", "YL7482", etc. are mentioned.

Specific examples of polyvinyl acetal resins include Denkabutyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisugagaku Kogyo Co., Ltd. Esrek BH series, BX series, KS series, BL series, BM series, etc. are mentioned.

As for content of a thermoplastic resin, 0.5-15 mass% is preferable with respect to 100 mass% of non volatile components in a 1st layer. The same range is preferable for a 2nd layer.

(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 the sum total of the non volatile component of an epoxy resin and an active ester compound 100 mass%, 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 resin composition of the present invention further contains a curing agent such as a phenol resin, a cyanate ester resin, a benzoxazine resin, a flame retardant such as a phosphorus compound, a metal hydroxide, an organic filler such as silicone powder, nylon powder, fluorine powder, rubber particles, An organic solvent, an additive, etc. can be mix | blended suitably.

The resin composition of this invention mixes the said components suitably, and also knead | mixes by mixing 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, as needed. Or it can manufacture as resin varnish by mixing.

[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, although it can set suitably in the range of 1 to 60 minutes at 80-170 degreeC, 1 to 30 minutes are preferable at 80-130 degreeC.

In order to lower the dielectric tangent of a resin sheet and to improve plating peeling strength, 2 micrometers or more are preferable for the thickness of a 1st layer. More preferably, it is 2-50 micrometers, More preferably, it is 4-35 micrometers.

[Second layer]

The 2nd layer of this invention can be produced as a resin composition layer which layered the resin composition on a 1st layer. Drying conditions etc. can be set suitably like a 1st layer.

In order to lower the thermal expansion coefficient of a resin sheet and to improve smear removal property, 2 micrometers or more are preferable for the thickness of a 2nd layer. More preferably, it is 2-50 micrometers, More preferably, it is 4-35 micrometers.

[Production Method of Resin Sheet with Support]

Various methods can be used as a manufacturing method of the resin sheet with a support body. 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. Moreover, while apply | coating a resin composition on a support body, you may apply another resin composition on it at the same time, and then dry it, and you can create a 1st layer and a 2nd layer simultaneously.

Although the ratio of the thickness of a 1st layer and a 2nd layer can be suitably set according to required performance, it is preferable that it is 1: 9-9: 1, and it is more preferable that it is 3: 7-7: 3.

[Multilayer printed wiring board using resin sheet with support]

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

In the manufacturing method of the multilayer printed wiring board of this invention, the process of laminating | stacking (A) the resin sheet with a support body on one side or both surfaces of an inner-layer circuit board, (B) the process of thermosetting a resin sheet with a support body, and forming an insulating layer, (C) forming a through hole by drilling the insulating layer, (D) peeling the support body, (E) roughening the surface of the insulating layer, (F) plating on the insulating layer surface after roughening the conductor And forming a layer.

(A) In the process of laminating the resin sheet with a support on one side or both sides of the inner layer circuit board (step (A)), the second layer of the resin sheet with the support is placed on the inner side circuit board side, and on one side or both sides of the inner layer circuit board. Laminated. 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 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 resin sheet with a support has a protective film, after removing the protective film, the resin sheet with a support and the inner layer circuit board are preheated as necessary, and the resin sheet with a support is pressurized and heated. While pressing on the inner circuit board. In the resin sheet with a support body of this invention, the method of laminating | stacking on 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 x 10 ⁴ N / m 2), and the compression time (lamination time) is preferably 5 to 180 seconds, and is preferably laminated under 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, a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meike Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, Ltd., Hitachi AIC Co., Ltd. ) Vacuum laminator and the like.

In the step (B) of thermosetting the resin sheet with a support to form an insulating layer (step (B)), after laminating the resin sheet with a support on the inner layer circuit board, the resin sheet is thermally cured to form an insulating layer on the inner layer circuit board. (Cured product) can be formed. 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 150-220 degreeC, More preferably, it is in the range of 30 to 120 minutes at 160-210 degreeC. Is selected. Moreover, by thermosetting without peeling a support body, foreign matter adhesion, such as dust and dust, during thermosetting can be prevented.

It is preferable that the resin sheet is thermosetted to form an insulating layer, and the coefficient of linear thermal expansion of the insulating layer is 25 ppm or less, more preferably 20 ppm or less. Although there is no restriction | limiting in particular in a lower limit, Usually, it is 4 ppm. Thereby, deformation of a buildup layer and wiring can be prevented, and a highly reliable multilayer printed wiring board can be obtained.

The resin sheet is thermally cured to form an insulating layer, and the dielectric loss tangent (measuring frequency 5.8 GHz) of the insulating layer is preferably 0.0065 or less, more preferably 0.006 or less. Although there is no restriction | limiting in particular in a lower limit, Generally, it is 0.001. Thereby, a multilayer printed wiring board with little electrical signal loss can be obtained.

(C) In the step of forming a via hole by drilling in the insulating layer (step (C)), the via hole is formed by drilling in 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 and combining these methods as needed, the drilling process by lasers, such as a carbon dioxide laser and a YAG laser, is preferable. In view of versatility, a carbon dioxide gas laser is more preferable.

When via holes are formed 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 via holes to be formed and the hole diameter. In order to increase the processing speed of the via hole and to improve the productivity of the multilayer printed wiring board, the short number is better, and the short number is preferably 1 to 3. In addition, when processing into several shots, the burst mode which is a continuous short may be sufficient, and the cycle mode which is a multiple shot which provided the time interval may be sufficient.

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. From the point of view of efficiency, 10 to 26 mu sec is more preferable.

In the case of punching with a carbon dioxide laser, in the resin sheet with a support of the present invention, it is preferable to adjust the laser energy to 0.1 to 3 W, and to adjust to 0.3 to 2 W from the viewpoint of improving the smear removal property. More preferred.

Since the resin sheet with a support body of this invention improves smear removal property, even if the top diameter (diameter) of the via hole of an insulating layer is made into small diameter, favorable drilling process is possible for thinning a multilayer printed wiring board. Specifically, in the step (C), the top diameter (diameter) of the via hole of the insulating layer is preferably 65 µm or less, more preferably 60 µm or less, further preferably 55 µm or less. On the other hand, in order to prevent becoming difficult to perform the roughening process in a via hole, it is preferable to make the top diameter (diameter) of a via hole into 15 micrometers or more.

(D) At a process ((D) process) which peels a support body, 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 addition, although (D) process may be performed before (C) process and (C) process, it is preferable to perform (C) process before (D) process from the point of smear removal property improvement.

(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 via hole 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 alkali solution. Examples of the alkali solution include sodium hydroxide solution and 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.

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. The concentration of 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.

The surface roughness after thermally curing the resin sheet to form an insulating layer, and roughening the surface of the insulating layer, preferably, the arithmetic mean roughness Ra is 150 nm or less for improving fine wiring formation, and 100 nm or less It is more preferable. Although there is no restriction | limiting in the lower limit of arithmetic mean roughness Ra, Usually, it is 10 nm or more. The root mean square roughness Rq is preferably 220 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and even more preferably 100 nm or less. Although there is no restriction | limiting in the lower limit of the root mean square roughness Rq, Usually, it becomes 20 nm or more. In addition, since the root mean square roughness Rq reflects the local state of the surface of an insulating layer, it can confirm that it is a more dense and smooth insulating layer surface by grasping Rq.

(F) In the process (plating F) of 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 dry plating, well-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. . As a pattern formation method after that, the subtractive method, the semiadditive method, etc. which are known to a person skilled in the art can be used, for example.

As for the peeling strength of the conductor layer and the said insulating layer which are obtained by thermosetting a resin sheet, forming an insulating layer, roughening the surface of the insulating layer, and plating, it is preferable that 0.5 kgf / cm or more. Although there is no restriction | limiting in particular in an upper limit, Usually, it is 1.2 kgf / cm.

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. The present invention can be suitably used as a resin sheet with a support for a buildup layer of a multilayer printed wiring board in view of excellent smear removability and plating peel strength despite low dielectric loss tangent and coefficient of thermal expansion.

<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, and a bumpless build-up layer The mounting method by (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonelectroconductive film (NCF), etc. are mentioned.

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. 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.

<Preparation of a sample for measurement of arithmetic mean roughness (Ra value), root mean square roughness (Rq value) and peel strength>

(1) ground treatment of inner layer circuit board

Both surfaces of the glass cloth base epoxy resin double-sided copper clad laminate (18 micrometers thickness of copper foil, 0.3mm of substrate thickness, R5715ES of Matsushita Denko Co., Ltd.) which formed an inner layer circuit were etched by 1 micrometer with CZ8100 by Merck Co., Ltd. The roughening process of the copper surface was performed.

(2) Lamination of Resin Sheet with Support

The resin sheet with a support body created in the Example and the comparative example was laminated on both surfaces of an inner layer circuit 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 | bonding at 100 degreeC and a pressure of 0.74 Mpa for 30 second after that.

(3) Curing of resin composition

The laminated adhesive film was cured at 80 ° C for 30 minutes, followed by curing conditions at 170 ° C and 30 minutes to form an insulating layer.

(4) via hole formation

Hitachi Via Mechanics, Ltd., using a CO ₂ laser processing machine (LC-2E21B / 1C) for producing a mask diameter of 1.60mm, the focus offset value is 0.050, the pulse width of 25μs, power 0.66W, the aperture 13, the short number 2, The insulating layer was drilled under the conditions of the burst mode, and the via hole whose top diameter (diameter) of the via hole in the insulating layer surface was 50 micrometers was formed. Thereafter, the PET film was peeled off.

(5) Harmonization processing

Atotech Japan Co., Ltd. diethylene glycol monobutyl ether containing swelling dip security P (glycol ether, aqueous solution of sodium hydroxide) which is a swelling liquid was used at 60 degreeC for 10 inner circuit boards which formed the insulating layer. It was immersed for minutes, and then, as a roughening liquid, it was immersed for 20 minutes at 80 degreeC in the condensate compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) of Atotech Japan Co., Ltd., and finally as a neutralizing liquid. 5 minutes was soaked in Atotech Japan Co., Ltd. Reduction Solleucine Securigant P (aqueous solution of sulfuric acid) at 40 ° C. for 5 minutes and then dried at 80 ° C. for 30 minutes. This board | substrate was made into evaluation board | substrate A.

(6) Plating by semi-additive process

The evaluation board A, electroless immersion for 5 minutes at 40 ℃ in the plating solution for containing PdCl _2, and the electroless plating in the following were immersed for 20 minutes at 25 ℃ the copper plating solution. After annealing by heating at 150 degreeC for 30 minutes, an etching resist was formed, copper sulfate electroplating was performed after the pattern formation by etching, and the conductor layer was formed in the thickness of 30 micrometers. Next, annealing was performed at 200 degreeC for 60 minutes. This substrate was used as evaluation substrate B.

<Measurement and evaluation of arithmetic mean roughness (Ra value), root mean square roughness (Rq value)>

Using the non-contact surface roughness machine (WYKO NT3300, manufactured by Noncoinstrument Co., Ltd.), the evaluation substrate A was obtained by using a VSI contact mode and a value obtained by setting the measurement range to 121 μm × 92 μm by a 50x lens, and the Ra value and Rq. The value was obtained. Each was measured by obtaining ten randomly chosen average values. The evaluation is as follows.

○: Ra value is 150 nm or less

X: Ra value is larger than 150 nm

○: Rq value is 220 nm or less

X: Rq value is larger than 220 nm

<Measurement and Evaluation of Peel Strength (Peel Strength) of Plating Conductor Layer>

A part notch of width 10mm and length 100mm was put in the conductor layer of the evaluation board B, and this end was peeled off, and it clamped with tongs (T.S.E., an autocommercial tester AC-50C-SL), and 50mm in room temperature. The load (kgf / cm) when 35 mm was peeled off in the vertical direction at the rate of / min was measured. The evaluation is as follows.

○: peel strength 0.5 kgf / cm or more

X: peel strength less than 0.5kgf / cm

<Evaluation of Smear Removability at the Bottom of Via Hole>

The circumference of the via hole bottom was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the via hole bottom was measured from the obtained image. The evaluation is as follows.

?: The maximum smear length was less than 3 占 퐉

X: Maximum smear length is 3 占 퐉 or more

Measurement and Evaluation of Coefficient of Thermal Expansion

The resin sheet with a support body obtained in the Example and the comparative example was thermosetted by heating at 200 degreeC for 90 minutes, and the sheet-form hardened | cured material was obtained by peeling a PET film. The hardened | cured material was cut into the test piece of about 5 mm in width and about 15 mm in length, and the thermomechanical analysis was performed by the tension-weighting method using the thermomechanical analyzer Thermo Plus TMA8310 (made by Rigaku Corporation). After the test piece was mounted on the above apparatus, the test piece was continuously measured twice under the conditions of a load of 1 g and a heating rate of 5 캜 / min. The average linear thermal expansion coefficient (ppm) from 25 degreeC to 150 degreeC in the 2nd measurement was computed. The evaluation is as follows.

○: average coefficient of linear thermal expansion less than 20 ppm

(Triangle | delta): An average linear thermal expansion coefficient of 20 ppm or more and 25 ppm or less

X: average linear thermal expansion coefficient is larger than 25 ppm

Measurement and Evaluation of Dielectric Junctions

The sheet-like hardened | cured material was obtained by heat-hardening by peeling a support body by heating the resin sheet with a support body obtained in the Example and the comparative example at 200 degreeC for 90 minutes. The hardened | cured material was cut out to length 80mm and width 2mm, and it was set as the evaluation sample. About this evaluation sample, the dielectric tangent was measured by the cavity resonance perturbation method at the measurement frequency of 5.8 GHz and the measurement temperature of 23 degreeC using the HP8362B apparatus by Agilent Technologies. Two test pieces were measured and the average value was computed. The evaluation is as follows.

○: dielectric loss tangent is 0.0065 or less

X: dielectric loss tangent is greater than 0.0065

<Adjustment of resin varnish 1>

5 parts of bisphenol-type epoxy resin ("XX1059" made by Shin-Nitetsu Chemical Co., Ltd., 1: 1 mixed product of bisphenol A type and bisphenol F type), crystalline bifunctional epoxy resin (Mitsubishi Chemical Co., Ltd. product) `` YX4000HK '', 10 parts of epoxy equivalent approximately 185), 10 parts of biphenyl type epoxy resin (`` NC3000H '' of Nihon Kayaku Co., Ltd.), phenoxy resin (YL7553BH30 manufactured by Mitsubishi Chemical Co., Ltd.), solid content 10 parts of 30 mass% MEK solution) was heat-dissolved, stirring 30 parts of solvent naphtha. After cooling to room temperature, there are 40 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Corporation, a toluene solution of 65% by mass of nonvolatile matter having an active group equivalent of about 223), a curing accelerator (4-dimethylaminopyridine, 7 parts of MEK solution of 2 mass% of solid content, flame retardant ("HCA-HQ" of Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphapé) Spherical silica (average particle diameter: 0.5 µm), surface-treated with 2 parts of ntrylene-10-oxide, 2 µm average particle diameter, and a phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") Note) "SOC2" manufactured by Ado-Matex, 160 parts of carbon amount per unit area of 0.39 mg / m 2) was mixed and uniformly dispersed with a high speed rotary mixer to prepare a resin varnish 1. The active ester compound was 12 mass%.

<Adjustment of resin varnish 2>

5 parts of bisphenol-type epoxy resin ("XX1059" made by Shin-Nitetsu Chemical Co., Ltd., 1: 1 mixed product of bisphenol A type and bisphenol F type), crystalline bifunctional epoxy resin (Mitsubishi Chemical Co., Ltd. product) `` YX4000HK '', 10 parts of epoxy equivalent approximately 185), 10 parts of biphenyl type epoxy resin (`` NC3000H '' of Nihon Kayaku Co., Ltd.), phenoxy resin (YL7553BH30 manufactured by Mitsubishi Chemical Co., Ltd.), solid content 10 parts of 30 mass% MEK solution) was heat-dissolved, stirring 30 parts of solvent naphtha. After cooling to room temperature, there are 20 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Corporation), a toluene solution of 65% by mass of nonvolatile matter having an active group equivalent of about 223), and a naphthol-based curing agent (hydroxyl equivalent 215, sinnet). 12 parts of MEK solution of 60% of solid content of "SN-485" made by Tetsugagaku Co., Ltd., 4 parts of hardening accelerator (4-dimethylaminopyridine, MEK solution of 2 mass% of solid content), flame retardant (Sanko Corporation) "HCA-HQ" of the manufacture, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphazanthrene-10-oxide, average particle diameter 2 micrometers) 2 parts, phenyl Spherical silica (average particle diameter 0.5 µm, "SOC2" manufactured by Adomatex Co., Ltd.), surface treated with an aminosilane-based coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573"), 0.39 mg of carbon per unit area / M 2) 150 parts were mixed and uniformly dispersed with a high speed rotary mixer to prepare a resin varnish 2. The active ester compound was 6.5 mass%.

<Adjustment of resin varnish 3>

5 parts of bisphenol-type epoxy resin ("XX1059" made by Shin-Nitetsu Chemical Co., Ltd., 1: 1 mixed product of bisphenol A type and bisphenol F type), crystalline bifunctional epoxy resin (Mitsubishi Chemical Co., Ltd. product) `` YX4000HK '', 10 parts of epoxy equivalent approximately 185), 10 parts of biphenyl type epoxy resin (`` NC3000H '' of Nihon Kayaku Co., Ltd.), phenoxy resin (YL7553BH30 manufactured by Mitsubishi Chemical Co., Ltd.), solid content 10 parts of 30 mass% MEK solution) was heat-dissolved, stirring 30 parts of solvent naphtha. After cooling to room temperature, there are 10 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Corporation, a toluene solution of 65% by mass of nonvolatile matter having an active group equivalent of about 223), and a triazine-containing phenolic curing agent (hydroxyl equivalent) 146, 10 parts of MEK solution of 60% of solid content of "LA-1356" of DIC Corporation), 3 parts of hardening accelerators (4-dimethylaminopyridine, MEK solution of 2 mass% of solid content), flame retardant (Sanko Corporation) "HCA-HQ" of the manufacture, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphazanthrene-10-oxide, average particle diameter 2 micrometers) 2 parts, phenyl Spherical silica (average particle diameter 0.5 µm, "SOC2" manufactured by Adomatex Co., Ltd.), surface treated with an aminosilane-based coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573"), 0.39 mg of carbon per unit area / M 2) 140 parts were mixed and uniformly dispersed with a high speed rotary mixer to prepare a resin varnish 3. The active ester compound was 3.6 mass%.

&Lt; Example 1 >

(Production of Resin Sheet 1 with Support)

Resin varnish 1 was applied by a die coater to a release surface of ETFE-treated release PET ("Fluoroju RL50KSE" manufactured by Mitsubishi Jushi Co., Ltd., 50 µm thick) so that the resin composition layer thickness after drying was 15 µm, and 100 It dried at 1 degreeC. Furthermore, the resin varnish 3 is apply | coated with a die coater on the resin composition layer so that the total thickness of the resin composition layer after drying may be set to 30 micrometers, it is dried at 80-120 degreeC (average 100 degreeC) for 4 minutes, and the resin surface of 15 micrometers in thickness is carried out. The resin sheet with a support body of the structure called a polypropylene cover film ("Alfan MA-411" manufactured by Ojitokushu Co., Ltd.) was bonded together, and called a release PET / resin composition layer 1 / resin composition layer 3 / cover film. Got.

<Example 2>

(Production of Resin Sheet 2 with Support)

In the same manner as in Example 1, a resin sheet with a support having a structure called a release PET / resin composition layer 2 / resin composition layer 3 / cover film was obtained.

&Lt; Comparative Example 1 &

(Production of Resin Sheet 3 with Support)

Release PET was carried out in the same manner as in Example 1 except that the resin varnish 1 was applied with a die coater so that the resin composition layer thickness after drying was 30 μm on the release PET, and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes. The resin sheet with a support body of the structure called / resin composition layer 1 / cover film was obtained.

Comparative Example 2

(Production of Resin Sheet 4 with Support)

Release PET was carried out in the same manner as in Example 1 except that the resin varnish 2 was applied with a die coater so as to have a thickness of the dried resin composition layer after drying on the release PET and dried at 80 to 120 ° C (average 100 ° C) for 5 minutes. The resin sheet with a support body of the structure called / resin composition layer 2 / cover film was obtained.

&Lt; Comparative Example 3 &

(Production of Resin Sheet 5 with Support)

Release PET was carried out in the same manner as in Example 1 except that the resin varnish 3 was applied with a die coater so as to have a thickness of the dried resin composition layer after drying on the release PET and dried at 80 to 120 ° C (average 100 ° C) for 5 minutes. The resin sheet with a support body of the structure called / resin composition layer 3 / cover film was obtained.

The evaluation results are shown in Table 1.

As is apparent from the results of Table 1, the resin sheets with a support of Examples 1 and 2 exhibited excellent characteristics. On the other hand, smear removal property was bad in Comparative Examples 1 and 2. In Comparative Example 3, the surface roughness was large, the peel strength was low, and the dielectric tangent was also increased.

In the present invention, it is possible to provide a resin sheet with a support having excellent smear removability and plating peel strength despite the low dielectric loss tangent and the coefficient of linear thermal expansion. 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 (14)

With a support,
A first layer containing an epoxy resin, an active ester compound, and an inorganic filler formed on the support, wherein the non-volatile component in the first layer is 100 mass%, the first layer having an active ester compound of 5 mass% or more,
A second layer containing an epoxy resin, an active ester compound and an inorganic filler formed on the first layer, wherein the non-volatile component in the second layer is 100 mass%, the second layer having an active ester compound of 5 mass% or less It has a resin sheet with a support body characterized by the above-mentioned. The resin sheet with a support according to claim 1, wherein the average particle diameter of the inorganic filler is 0.01 to 3 µm. The content of the said inorganic filler is 40-90 mass%, The resin sheet with a support body of Claim 1 characterized by the above-mentioned. The resin sheet with a support according to claim 1, wherein the inorganic filler is surface treated with a surface treating agent. The resin sheet with a support according to claim 4, wherein the carbon amount per unit surface area of the inorganic filler is 0.02 to 1 mg / m 2. The thickness of the said 2nd layer is 2 micrometers or more, The resin sheet with a support body of Claim 1 characterized by the above-mentioned. The resin sheet with a support according to claim 1, wherein the resin sheet is thermally cured to form an insulating layer, and the coefficient of linear thermal expansion of the insulating layer is 25 ppm or less. The resin sheet with a support according to claim 1, wherein the resin sheet is thermally cured to form an insulating layer, and the dielectric tangent (measuring frequency of 5.8 GHz) of the insulating layer is 0.0065 or less. The arithmetic mean roughness Ra after the heat treatment of the resin sheet to form an insulating layer, and the surface of the insulating layer is roughened is 150 nm or less, and the root mean square roughness Rq is 220 nm or less. The resin sheet with a support body characterized by the above-mentioned. 2. The peel strength of the conductor layer and the insulating layer obtained by heat curing the resin sheet to form an insulating layer, roughening the surface of the insulating layer and plating, and having a peel strength of 0.5 kgf / cm or more. Resin sheet with a support. The resin sheet with a support according to any one of claims 1 to 10, which is a resin sheet with a support for an insulating layer of a multilayer printed wiring board. It is a resin sheet with a support body for buildup layers of a multilayer printed wiring board, The resin sheet with a support body in any one of Claims 1-10 characterized by the above-mentioned. (A) Process of laminating | stacking the resin sheet with a support body in any one of Claims 1-10 on one side or both sides of an inner layer circuit board,
(B) thermosetting the resin sheet with a support to form an insulating layer,
(C) perforating the insulating layer to form via holes,
(D) peeling off the support;
(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 via hole by drilling in the insulating layer (C), the top diameter (diameter) of the via hole of the insulating layer is 65 µm or less, characterized in that the method for manufacturing a multilayer printed wiring board. The semiconductor device manufactured using the multilayer printed wiring board manufactured by the method of Claim 13.