WO2013176224A1

WO2013176224A1 - Method for manufacturing multilayer printed wiring board

Info

Publication number: WO2013176224A1
Application number: PCT/JP2013/064386
Authority: WO
Inventors: 亮宮本; 弘久奈良橋; 中村　茂雄
Original assignee: 味の素株式会社
Priority date: 2012-05-23
Filing date: 2013-05-23
Publication date: 2013-11-28
Also published as: JP6281489B2; TW201412217A; JPWO2013176224A1; TWI605742B

Abstract

Provided is a method for manufacturing a multilayer printed wiring board which comprises an insulating layer that has a uniform thickness, high glass transition temperature, low linear thermal expansion coefficient and less voids. This method for manufacturing a multilayer printed wiring board is characterized by comprising (A) a step wherein a prepreg with a supporting body is vacuum laminated on an inner circuit board by applying heat and pressure thereto and (B) a step wherein an insulating layer is formed by thermally curing the prepreg. This method for manufacturing a multilayer printed wiring board is also characterized in that: the prepreg contains a curable resin composition and a sheet-like fiber base; the content of the curable resin composition in the prepreg is from 30% by mass to 85% by mass (inclusive); the curable resin composition contains an inorganic filler; and, in the step (A), the degree of vacuum during the lamination is 0.001-0.40 kPa, the time to vacuum is 15 seconds or less, the pressure applied during the lamination is 1-16 kgf/cm², the heating temperature during the lamination is 60-160°C, and the time duration of the lamination is 10-300 seconds.

Description

Manufacturing method of multilayer printed wiring board

The present invention relates to a method for manufacturing a multilayer printed wiring board. Furthermore, the present invention relates to a semiconductor device using the multilayer printed wiring board.

A multilayer printed wiring board is used for an integrated circuit which is indispensable for a semiconductor device, and a metal-clad laminated board can be cited as a main component. As a method for producing the metal-clad laminate, a prepreg is prepared by cutting to an arbitrary size, one or several sheets of this are stacked, and a copper foil of the same size or larger than that of the prepreg is formed on the upper and lower sides thereof. Is generally used, and a vacuum press molding is performed by laminating the layers between hot plates.

In recent years, with the miniaturization and higher functionality of semiconductor devices, multilayer printed wiring boards have been required to be thinned while maintaining strength, not only in metal-clad laminates, but also in build-up layers, It is required to laminate a rigid prepreg. However, in the prepreg build-up lamination, it is difficult to maintain a balance between fluidity and embedding property due to the presence of the sheet-like fiber base material in the prepreg. In particular, when using a curable resin composition containing a high content (for example, 60% by mass or more) of an inorganic filler so as to reduce the linear thermal expansion coefficient of the obtained insulating layer, voids in the insulating layer are used. Problems such as generation and smoothness of the surface of the insulating layer become more obvious, and it becomes more difficult to maintain such a balance. In Patent Document 1, there is a description of stacking prepregs, but studies on the prepreg itself and the manufacturing method are scarce, and the performance of the multilayer printed wiring board is sufficient, such as a low glass transition temperature of the obtained insulating layer. It was not a thing.

JP 2009-49365 A

An object of the present invention is to provide a method for producing a multilayer printed wiring board having an insulating layer having a uniform film thickness with a high glass transition temperature, a low coefficient of linear thermal expansion, and suppressed voids.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be achieved by combining a specific prepreg and a specific vacuum lamination method.

The present invention includes the following aspects.
[1] (A) Step of heating and pressurizing the prepreg with a support to the inner layer circuit board for vacuum lamination,
(B) a step of thermosetting the prepreg to form an insulating layer;
A method for producing a multilayer printed wiring board, comprising:
The prepreg contains a curable resin composition and a sheet fiber substrate,
The content of the curable resin composition in the prepreg is 30% by mass or more and 85% by mass or less,
The curable resin composition contains an inorganic filler,
In step (A), the degree of vacuum during lamination is 0.001 to 0.40 kPa, the time to reach vacuum is 15 seconds or less, the pressure during lamination is 1 to 16 kgf / cm ² , and the heating temperature during lamination is 60 to A method for producing a multilayer printed wiring board, characterized in that the lamination time is 10 to 300 seconds at 160 ° C.
[2] The method for producing a multilayer printed wiring board according to the above [1], wherein the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1 is 0.25 to 0.88.
[3] The content ratio of the sheet-like fiber substrate and the inorganic filler in the prepreg (the mass of the sheet-like fiber substrate / the mass of the inorganic filler) is 0.2 to 2.5. The manufacturing method of the multilayer printed wiring board as described in said [1] or [2].
[4] The above-mentioned [1] to [3], wherein the sheet-like fiber base material contains one or more selected from the group consisting of glass cloth, glass nonwoven fabric, organic woven fabric, and organic nonwoven fabric. The manufacturing method of the multilayer printed wiring board in any one.
[5] Any of the above [1] to [3], wherein the sheet-like fiber substrate contains one or more selected from the group consisting of E glass fiber, S glass fiber and Q glass fiber A method for producing a multilayer printed wiring board according to claim 1.
[6] The method for producing a multilayer printed wiring board according to any one of [1] to [5], wherein the inorganic filler has an average particle size of 0.01 to 2 μm.
[7] The method for producing a multilayer printed wiring board according to any one of [1] to [6], wherein the inorganic filler has an average particle size of 0.01 to 0.4 μm.
[8] The above-mentioned [1] to [7], wherein the content of the inorganic filler is 40 to 85% by mass when the nonvolatile component in the curable resin composition is 100% by mass. The manufacturing method of the multilayer printed wiring board in any one.
[9] The content of the inorganic filler is 60 to 85% by mass when the nonvolatile component in the curable resin composition is 100% by mass, according to the above [1] to [8] The manufacturing method of the multilayer printed wiring board in any one.
[10] In the step (A),
When the protective film is attached to the prepreg with the support wound in a roll shape, the protective film is peeled off and sequentially supplied to the vacuum laminator, and the prepreg surface of the prepreg with the support faces the inner circuit board. The method for producing a multilayer printed wiring board according to any one of the above [1] to [9], wherein a prepreg with a support is vacuum laminated on an inner circuit board by heating and pressurizing using a vacuum laminator .
[11] In the step (B),
The method for producing a multilayer printed wiring board according to any one of [1] to [10] above, wherein the temperature at the time of thermosetting is 150 to 250 ° C. and the time at the time of thermosetting is 30 to 300 minutes.
[12] In the step (B),
The method for producing a multilayer printed wiring board according to any one of the above [1] to [11], wherein the insulating layer is formed by thermosetting the prepreg using a heating oven.
[13] In the step (B),
The method for producing a multilayer printed wiring board according to any one of the above [1] to [12], wherein the prepreg is arranged in a vertical state in a heating oven and thermally cured to form an insulating layer.
[14] In the step (B),
The multilayer printed wiring board is fixed with a heat-resistant jig, the prepreg is heat-cured, and the multilayer printed wiring board inside the jig is cut out after being cured, according to any one of the above [1] to [13] A method for producing a multilayer printed wiring board.
[15] The method for producing a multilayer printed wiring board according to any one of [1] to [14], wherein the insulating layer has a linear thermal expansion coefficient of 15 ppm or less.
[16] The method for producing a multilayer printed wiring board according to any one of [1] to [15], wherein the insulating layer has a glass transition temperature of 181 ° C. or higher.
[17] The method for producing a multilayer printed wiring board according to any one of [1] to [16], further comprising (C) a step of peeling the support.
[18] The method for producing a multilayer printed wiring board according to any one of [1] to [17], further comprising (D) a step of forming a via hole.
[19] The method for producing a multilayer printed wiring board according to any one of [1] to [18], further comprising (E) a desmear process.
[20] The method for producing a multilayer printed wiring board according to any one of [1] to [19], further comprising (F) a step of forming a conductor layer by plating.
[21] A semiconductor device comprising a multilayer printed wiring board obtained by the manufacturing method according to any one of [1] to [20].

According to the present invention, by combining a specific prepreg and a specific vacuum laminating method, a multilayer printed wiring having an insulating layer with a uniform film thickness that has a high glass transition temperature, a low linear thermal expansion coefficient, and a suppressed void. A method for manufacturing a plate can be provided.

Hereinafter, the present invention will be described in detail on the basis of preferred embodiments thereof.

The present invention
(A) A step of heating and pressurizing the prepreg with a support to the inner layer circuit board to perform vacuum lamination,
(B) a step of thermosetting the prepreg to form an insulating layer;
A method for producing a multilayer printed wiring board, comprising:
The prepreg contains a curable resin composition and a sheet fiber substrate,
The content of the curable resin composition in the prepreg is 30% by mass or more and 85% by mass or less,
The curable resin composition contains an inorganic filler,
In the step of (A) heating and pressurizing the prepreg with a support on the inner layer circuit board for vacuum lamination, the degree of vacuum during lamination is 0.001 to 0.40 kPa, the time to reach vacuum is 15 seconds or less, and A method for producing a multilayer printed wiring board, wherein the pressure is 1 to 16 kgf / cm ² , the heating temperature during lamination is 60 to 160 ° C., and the time during lamination is 10 to 300 seconds.

<(A) Process>
The step (A) is a step of heating and pressurizing the prepreg with a support on the inner layer circuit board to perform vacuum lamination. The prepreg used in the present invention contains a curable resin composition and a sheet-like fiber base material.

[Curable resin composition]
The curable resin composition can be used without any particular limitation. Among them, (c) a composition containing an inorganic filler is preferable, and (a) an epoxy resin and (c) a composition containing an inorganic filler are more preferable. More preferably, the composition contains (a) an epoxy resin, (b) a curing agent, and (c) an inorganic filler. (a) As an epoxy resin, for example, bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, alicyclic Epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, epoxy resin having butadiene structure, Diglycidyl etherified products of bisphenols, diglycidyl etherified products of naphthalene diol, glycidyl etherified products of phenols, and diglycidyl etherified products of alcohols, Alkyl-substituted bodies of these epoxy resins, halides and hydrogenated products, and the like in. These may be used alone or in combination of two or more.

Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type from the viewpoint of improving heat resistance, improving insulation reliability, improving mechanical properties, and improving adhesion to metal foil (conductor layer). Epoxy resins, naphthylene ether type epoxy resins, glycidyl ester type epoxy resins, and epoxy resins having a butadiene structure are preferable, and bisphenol A type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins are more preferable. . Specifically, for example, liquid bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation), naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS” manufactured by DIC Corporation)) Naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), naphthol type epoxy resin (“ESN-475V” manufactured by Tohto Kasei Co., Ltd.), naphthylene ether type epoxy resin (DIC Corporation) ) “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3”), glycidyl ester type epoxy resin (“EX711”, “EX721”, manufactured by Nagase ChemteX Corp.) ) "R540" made by Printec), epoxy resin with butadiene structure ( Iseru Chemical Industry Co., "PB-3600" manufactured), biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000H", "NC3000L", Mitsubishi Chemical Co., Ltd. "YX4000") and the like.

(a) From the viewpoint of improving mechanical properties, the upper limit value of the content of the epoxy resin is preferably 40% by mass or less, more preferably 30% by mass or less, when the nonvolatile component in the curable resin composition is 100% by mass. Preferably, 20 mass% or less is more preferable. On the other hand, the lower limit of the content of the epoxy resin is 1 when the nonvolatile component in the curable resin composition is 100% by mass from the viewpoints of improving heat resistance, improving insulation reliability, and improving adhesion to the metal foil. % By mass or more is preferable, 3% by mass or more is more preferable, and 5% by mass or more is more preferable. Further, it is preferable to use a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, in which case the liquid epoxy resin is suitable for improving the flexibility of the prepreg and enabling a vacuum lamination method in the prepreg. Yes, a solid epoxy resin is suitable for imparting the rigidity of the prepreg. From such a viewpoint, the mixing ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1: 2 by mass ratio, The range of 1: 1.8 is more preferable, and the range of 1: 0.6 to 1: 1.5 is more preferable.
In the present invention, “liquid epoxy resin” refers to an epoxy resin that is liquid at a temperature of 20 ° C., and “solid epoxy resin” refers to an epoxy resin that is solid at a temperature of 20 ° C.

(b) As the curing agent, for example, a phenolic curing agent, an active ester curing agent, a cyanate ester curing agent, a benzoxazine curing agent, an acid anhydride curing agent, an amine curing agent, a guanidine curing agent, Examples thereof include imidazole-based curing agents, and epoxy adducts and microencapsulated products thereof. These may be used alone or in combination of two or more.

Among these, phenol-based curing agents, active ester-based curing agents, and cyanate ester-based curing agents are preferable from the viewpoints of improving heat resistance and improving adhesion to a metal foil (conductor layer).

The phenolic curing agent is not particularly limited, but a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolac type curing agent, a naphthylene ether type curing agent, and a triazine skeleton-containing phenolic curing agent are preferable. Specifically, MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.) as biphenyl type curing agents, NHN, CBN, GPH (Nippon Kayaku Co., Ltd.) as naphthalene type curing agents, SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), EXB9500 (manufactured by DIC Corporation), TD2090 (manufactured by DIC Corporation) as a phenol novolac type curing agent, naphthylene Examples of the ether type curing agent include EXB-6000 (manufactured by DIC Corporation). Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation) and the like. In particular, a triazine skeleton-containing phenolic curing agent is preferable in terms of improving the appearance.

Active ester curing agents generally include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds. Is preferably used. The active ester compound is preferably an active ester compound obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. You may use an active ester compound individually by 1 type or in combination of 2 or more types. As the active ester compound, an active ester compound disclosed in JP-A-2004-277460 may be used, or a commercially available active ester compound may be used. Examples of commercially available active ester compounds include active ester compounds containing a dicyclopentadienyl diphenol structure, acetylated phenol novolacs, and benzoylated phenol novolacs. Specifically, for example, EXB-9451 and EXB-9460 (manufactured by DIC Corporation) as active ester compounds having a dicyclopentadienyl diphenol structure, DC808 as an acetylated product of phenol novolac, and a benzoylated product of phenol novolac YLH1026 (manufactured by Mitsubishi Chemical Corporation) and the like.

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

Specific examples of the benzoxazine-based curing agent include Fa, Pd (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like.

The blending ratio of (a) epoxy resin and (b) curing agent is preferably such that when the number of epoxy groups of the epoxy resin is 1, the number of reactive groups of the curing agent is in the range of 0.4 to 2.0. A ratio in the range of 5 to 1.0 is more preferable. The number of epoxy groups in the epoxy resin present in the curable resin composition is a value obtained by adding the values obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins. Further, the number of reactive groups of the curing agent is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all the curing agents. When the ratio of the reactive groups is within this range, the mechanical strength and water resistance of the cured product tend to be improved.

Examples of the inorganic filler (c) include silica, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, titanium oxide, and the like. Silica and alumina are preferable, and amorphous silica, fused silica, Silica such as crystalline silica, synthetic silica and hollow silica is preferred. As the silica, spherical silica is preferable. These may be used alone or in combination of two or more. Spherical fused silica is preferred from the viewpoint of improving the filling properties of the resin composition. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs Corporation.

(C) The upper limit of the average particle size of the inorganic filler is preferably 2 μm or less, from the viewpoint of improving the insulation reliability and improving the impregnation property of the resin varnish into the sheet-like fiber base material. Is more preferably 0.8 μm or less, still more preferably 0.6 μm or less, still more preferably 0.4 μm or less, and particularly preferably 0.3 μm or less. On the other hand, the lower limit of the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and more preferably 0.1 μm or more from the viewpoint of preventing aggregation of the inorganic filler and improving dispersibility. Is more preferable. In particular, an inorganic filler having an average particle diameter of 0.01 to 0.4 μm is used in combination from the viewpoint of improving the impregnation property of the resin varnish into the sheet-like fiber base material and reducing the linear thermal expansion coefficient of the insulating layer. It is more preferable to use an inorganic filler having an average particle size of 0.01 to 0.3 μm in combination. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

(C) The content of the inorganic filler is a non-volatile component in the curable resin composition from the viewpoint of improving the impregnation property of the sheet-like fiber base material and the film thickness uniformity of the insulating layer. When it is 100 mass%, 85 mass% or less is preferable, and 80 mass% or less is more preferable. On the other hand, from the viewpoint of reducing the linear thermal expansion coefficient of the insulating layer and from the viewpoint of imparting rigidity to the insulating layer, when the non-volatile component in the curable resin composition is 100% by mass, (C) the inorganic filler The lower limit of the content is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more.

(C) Inorganic fillers are epoxy silane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate cups from the viewpoint of improving moisture resistance. It is preferable that the surface treatment is performed with a surface treatment agent such as a ring agent. You may use a surface treating agent individually by 1 type or in combination of 2 or more types. Specific examples of the surface treatment agent include aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, and the like. Aminosilane coupling agents, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Epoxysilane coupling agents, mercaptosilane coupling agents such as mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, methyltrimethoxysilane, octadecyl Silane coupling agents such as trimethoxysilane, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, hexamethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, 1,1,3 , 3,5,5-hexamethylcyclotrisilazane and other organosilazane compounds, butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium , Bis (dioctylpyrophosphate) ethylene titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium mono Tearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1- Butyl) bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, Isopropyltridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pi Phosphate) titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate coupling agents such as titanates. Of these, aminosilane coupling agents are preferred because of their excellent moisture resistance, dispersibility, and properties of cured products.

The curable resin composition may further contain (d) a thermoplastic resin from the viewpoint that moderate flexibility can be imparted to the prepreg. Examples thereof include phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone, polysulfone and the like. These may be used alone or in combination of two or more.

(d) From the viewpoint of improving heat resistance, the content of the thermoplastic resin is preferably 30% by mass or less, more preferably 20% by mass or less, when the nonvolatile component in the curable resin composition is 100% by mass. 10 mass% or less is still more preferable. Further, from the viewpoint of increasing the viscosity of the curable resin composition to obtain a prepreg (and thus an insulating layer) having a uniform film thickness, the lower limit of the content of the thermoplastic resin is (d) in the curable resin composition. When the non-volatile component is 100% by mass, 0.5% by mass or more is preferable, 1% by mass or more is more preferable, and 3% by mass or more is more preferable.

Examples of the phenoxy resin include “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YX8100”, “YL6954”, “YL6974”, “YL7213”, “YL6794”, “YL6794”, “Mitsubishi Chemical Co., Ltd.” YL7553 "," YL7482 ", etc. are mentioned. Examples of the polyvinyl acetal resin include Denki Butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., and Slekk BH Series, BX Series, and KS Series manufactured by Sekisui Chemical Co., Ltd. , BL series, BM series and the like, and polyvinyl butyral resin is preferable. Examples of the polyimide include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. As the polyimide, linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (as described in JP-A-2006-37083), a polysiloxane skeleton-containing polyimide (specialty) Examples thereof include modified polyimides such as those described in JP-A No. 2002-12667 and JP-A No. 2000-319386. Examples of the polyamideimide include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Examples of the polyamideimide include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd. Examples of polyethersulfone include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd. Examples of the polysulfone include “P1700” and “P3500” manufactured by Solven Advanced Polymers Co., Ltd.

The curable resin composition may further contain (e) a curing accelerator from the viewpoint of efficiently curing the epoxy resin and the curing agent. Examples include imidazole compounds, pyridine compounds, and organic phosphine compounds. Specific examples include 2-methylimidazole, 4-dimethylaminopyridine, and triphenylphosphine. These may be used alone or in combination of two or more. When (e) a curing accelerator is used, it is preferably used in the range of 0.1 to 3.0% by mass relative to (a) the epoxy resin.

The curable resin composition may further contain (f) rubber particles for the purpose of preventing cracking of the insulating layer and reducing the stress. The rubber particles do not dissolve in the organic solvent when preparing the curable resin composition, are not compatible with other components in the curable resin composition such as epoxy resin, and in the varnish of the curable resin composition Those present in a dispersed state are preferred. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles. Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a rubber particle having a two-layer structure in which an outer shell layer is a glassy polymer and an inner core layer is a rubbery polymer, Alternatively, rubber particles having a three-layer structure in which the shell layer of the outer layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer can be used. The glassy polymer is composed of, for example, a polymer of methyl methacrylate, and the rubbery polymer is composed of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (trade name of Ganz Kasei Co., Ltd.), and Metabrene KW-4426 (trade name of Mitsubishi Rayon Co., Ltd.). Specific examples of acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Methbrene W300A (average particle size 0.1 μm), W450A (average particle size 0.5 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

The curable resin composition includes a bismaleimide-triazine resin, an acrylic resin, a maleimide compound, a bisallylnadiimide compound, a vinyl benzyl resin, a vinyl benzyl ether resin, as long as the effects of the present invention are exhibited as necessary. You may mix | blend thermosetting resins other than epoxy resins, such as a block isocyanate compound, a flame retardant, etc. These may be used alone or in combination of two or more. As maleimide resins, BMI1000, BMI2000, BMI3000, BMI4000, BMI5100 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (manufactured by KEI Kasei Co., Ltd.), ANILIX-MI (Mitsui Chemical Fine) Manufactured by Co., Ltd.), BANI-M and BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.) as bisallylnadiimide compounds, V5000 (manufactured by Showa Polymer Co., Ltd.) and vinylbenzyl ether as vinylbenzyl resins. Examples of the resin include V1000X and V1100X (manufactured by Showa Polymer Co., Ltd.). Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. Examples of organophosphorus flame retardants include phosphine compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Fine Techno. Reefos 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ manufactured by Hokuko Chemical Co., Ltd., Clariant Phosphorus ester compounds such as OP930 manufactured by Daihachi Chemical Co., Ltd., PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289 manufactured by Toto Kasei Co., Ltd., and FX310, and phosphorus-containing phenoxy such as ERF001 manufactured by Toto Kasei Co. Examples thereof include resins. Examples of the organic nitrogen-containing phosphorus compound include phosphoric ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., and phosphazene compounds such as SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd. Examples of metal hydroxides include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308, B manufactured by Sakai Kogyo Co., Ltd. And aluminum hydroxide such as −303 and UFH-20.

The curable resin composition may also contain other components as long as the effects of the present invention are exhibited. Examples of such other components include fillers such as silicone powder, nylon powder and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based and polymer-based antifoaming agents or leveling agents, and imidazole. , Thiazole, triazole, silane coupling agents, etc., colorants such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, carbon black, ketones (acetone, methyl ethyl ketone, cyclohexanone) Etc.), acetates (ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.), carbitols (cellosolve, butyl carbitol, etc.), aromatic hydrocarbons (True) , Xylene), dimethylformamide, dimethylacetamide, organic solvents such as N- methylpyrrolidone, and the like.

The curable resin composition is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. Can be prepared. Further, it can be prepared as a resin varnish by further adding an organic solvent.

[Sheet fiber substrate]
The sheet-like fiber base material used for the prepreg is not particularly limited, and examples thereof include a glass fiber base material and an organic fiber base material, and in particular, one type selected from the group consisting of glass cloth, glass nonwoven fabric, organic woven fabric, and organic nonwoven fabric. It is preferable to contain the above. From the viewpoint of reducing the linear thermal expansion coefficient of the prepreg, a sheet fiber substrate such as a glass fiber substrate, an aramid nonwoven fabric, and a liquid crystal polymer nonwoven fabric is preferable, a glass fiber substrate is more preferable, and a glass cloth is more preferable. As a glass fiber used for a glass fiber base material, from a viewpoint that a linear thermal expansion coefficient can be reduced, 1 or more types of glass fibers selected from the group which consists of E glass fiber, S glass fiber, and Q glass fiber are included. Preferably, S glass fiber and Q glass fiber are more preferable, and Q glass fiber is still more preferable. Q glass fiber refers to glass fiber in which the content of silicon dioxide occupies 90% or more. The thickness of the sheet fiber substrate is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less, still more preferably 50 μm or less, and even more preferably 40 μm or less, from the viewpoint of reducing the thickness of the prepreg. Further, from the viewpoint of improving the handleability and the viewpoint of improving the rigidity of the prepreg, it is preferably 1 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more.

Specific examples of the sheet-like fiber base material are given below. As the glass cloth, for example, Style 1027MS (A warp density of 75/25 mm, a weft density of 75/25 mm, a fabric weight of 20 g / m ² , a thickness of 19 μm (E glass fiber)) manufactured by Asahi Schavel Co., Ltd. Co., Ltd. Style 1037MS (warp density 70/25 mm, weft density 73/25 mm, fabric weight 24 g / m ² , thickness 28 μm (E glass fiber)), 1078 manufactured by Arizawa Seisakusho (warp density) 54/25 mm, weft density 54/25 mm, fabric weight 48 g / m ² , thickness 43 μm (E glass fiber)), 2116 manufactured by Arisawa Manufacturing Co., Ltd. (warp density 50/25 mm, weft density 58 / 25 mm, fabric weight 103.8 g / m ² , thickness 94 μm (E glass fiber)), 1067 manufactured by Arisawa Manufacturing Co., Ltd. (warp density 70/25 mm, weft) Density 70 / 25mm, fabric weight 31g / m ² , thickness 33μm (E glass fiber)), quartz glass cloth (IPC standard 2116 type cloth and IPC standard 1035 type cloth (Q glass fiber) manufactured by Shin-Etsu Quartz Co., Ltd.) ), T glass cloth (IPC standard 1078, 1035, 1037, 1027 (T glass fiber)) manufactured by Nittobo. In addition, liquid crystal polymer non-woven fabrics include Vecrus (weighing 6 to 15 g / m ² ), which is a non-woven fabric manufactured from a polyarylate-based liquid crystal polymer manufactured by Kuraray Co., Ltd., and Vectran manufactured by Kuraray Co., Ltd. And non-woven fabrics.

[Support]
Although the support body used by this invention is not restrict | limited in particular, It is a film which has self-supporting property, A metal foil and a plastic film are used suitably. Examples of the metal foil include copper foil and aluminum foil. Examples of the plastic film include polyethylene terephthalate film, polyethylene naphthalate, polyimide, polyamideimide, polyamide, polytetrafluoroethylene, polycarbonate, and the like. Polyethylene terephthalate film and polyethylene naphthalate film are preferable, and polyethylene is inexpensive. A terephthalate film is more preferable. The plastic film is preferably a release plastic film subjected to surface treatment such as mat treatment or corona treatment for the purpose of improving the peelability after curing. In consideration of winding, surface treatment may be performed on both surfaces of the support. From the viewpoint of improving the film thickness uniformity of the prepreg, the surface of the support in contact with the prepreg preferably has a surface roughness (Ra value) of 50 nm or less, more preferably 40 nm or less, still more preferably 35 nm or less, and further preferably 30 nm or less. More preferred is 25 nm or less. The lower limit of the surface roughness (Ra value) is not particularly limited, but is preferably 0.1 nm or more and more preferably 0.5 nm or more from the viewpoint of practicality of the support. The surface roughness (Ra value) can be measured by using a known method, for example, by using a device such as a non-contact type surface roughness meter (for example, WYKO NT3300 manufactured by Beec Instruments). it can. The support may be a commercially available support, for example, T60 (manufactured by Toray Industries, Inc., polyethylene terephthalate film), A4100 (manufactured by Toyobo Co., Ltd., polyethylene terephthalate film), Q83 (manufactured by Teijin DuPont Films, Inc.) , Polyethylene naphthalate film), polyethylene terephthalate film with alkyd mold release agent (AL-5) manufactured by Lintec Corporation, Diafoil B100 (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., polyethylene terephthalate film), JTC foil (JX And Nippon Mining & Metals Co., Ltd. (thickness 18 μm), MT18Ex (manufactured by Mitsui Mining & Smelting Co., Ltd.) The thickness of the support is preferably 10 μm or more, more preferably 15 μm or more, from the viewpoint of improving the handleability of the support and improving the peelability of the support. Moreover, from a viewpoint of cost performance, 70 micrometers or less are preferable and 50 micrometers or less are more preferable.

[Prepreg with support]
The prepreg with a support used in the present invention is obtained by bonding a support to the prepreg surface. Therefore, in one embodiment, a prepreg with a support includes a support and a prepreg joined to the support. In the prepreg with a support, an ultrathin resin layer may be interposed between the support and the prepreg. Therefore, in another embodiment, the prepreg with a support includes a support, an ultrathin resin layer bonded to the support, and a prepreg bonded to the ultrathin resin layer. Here, the ultrathin resin layer refers to a resin layer (insulating layer) having a thickness of 1 to 10 μm and containing no sheet-like fiber base material. A method for producing the prepreg with a support is not particularly limited, and examples thereof include a hot melt method and a solvent method, and the following methods (i) to (iv) are preferable.

(I): a method in which a curable resin composition is once coated on a support without dissolving the curable resin composition in an organic solvent, and is laminated on a sheet-like fiber substrate (ii): a die coater or the like (Iii): Resin in which the curable resin composition is dissolved in an organic solvent. (Iii): A resin in which a curable resin composition is dissolved in an organic solvent. A method of preparing a varnish, immersing, impregnating and drying a sheet-like fiber base material into a resin varnish to form a prepreg, and then laminating the prepreg on the support (iv): using a die coater or the like on the support A method comprising directly applying a resin varnish to form a curable resin composition layer, and laminating the curable resin composition layer from both sides of a sheet-like fiber substrate. The group consisting of the above methods (i) to (iv) Than It is preferable to produce a prepreg with a support using one or more selected methods. In order to prevent dust and the like from adhering to the prepreg, a support may be bonded to the prepreg surface, and a protective film may be bonded to the other surface of the prepreg. The thing similar to a support body can be used for a protective film. When the prepreg with a support has an ultrathin resin layer, the prepreg with a support can be formed in the same manner as described above by forming an ultrathin resin layer on the support in advance. .

When a curable resin composition or a resin varnish is applied, it is necessary to dry the organic solvent. In the laminating process, as long as the curable resin composition has fluidity and adhesiveness, the drying conditions are as follows. There is no particular limitation. If a large amount of the organic solvent remains in the prepreg, it may cause blistering after curing. Therefore, a drying condition in which the content of the organic solvent in the curable resin composition is 0.05 to 5% by mass is preferable. A drying condition of 1 to 2% by mass is more preferable. Specific drying conditions vary depending on the curability of the curable resin composition and the amount of the organic solvent in the varnish, but it is preferable to dry at 80 to 180 ° C. for 3 to 13 minutes, and at 90 to 140 ° C. for 3 to 10 minutes. It is preferable to dry for a minute.

In the prepreg with a support, the thickness of the prepreg is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 40 μm or more, from the viewpoint of ensuring the rigidity desired as the prepreg. Moreover, from a viewpoint of making a multilayer printed wiring board into a thin film, 200 micrometers or less are preferable, 150 micrometers or less are more preferable, 100 micrometers or less are still more preferable, and 70 micrometers or less are still more preferable. In addition, the prepreg must have fluidity that can be laminated following the unevenness of the inner circuit board during lamination, and the minimum melt viscosity of the curable resin composition in the prepreg is in the range of 200 to 30000 poise. Is preferable, more preferably in the range of 500 to 20000 poise, and still more preferably in the range of 1000 to 10,000 poise.

Further, in order to increase the rigidity of the prepreg, the thickness of the sheet-like fiber base material (the thickness of the sheet-like fiber base material / the thickness of the prepreg) when the thickness of the prepreg is 1 is controlled to 0.25 to 0.88. It is preferable. From the viewpoint of increasing the rigidity of the prepreg and achieving a low linear thermal expansion coefficient, 0.3 or more is more preferable, 0.35 or more is further preferable, and 0.4 or more is even more preferable. Moreover, 0.85 or less is more preferable from the point which improves film thickness uniformity and suppresses appearance defect, and 0.80 or less is still more preferable.

In addition, the prepreg of the present invention has a curable resin composition content of 30 to 85 mass in the prepreg in order to achieve uniform thickness and thinning of the insulating layer while satisfactorily embedding the wiring pattern of the inner circuit board. % Is preferably controlled. From the viewpoint of reducing the linear thermal expansion coefficient and contributing to thinning, the content of the curable resin composition in the prepreg is more preferably 80% by mass or less, still more preferably 75% by mass or less, and 70% by mass or less. Is even more preferable, and 65% by mass or less is particularly preferable. Further, from the viewpoint of improving adhesion with the inner layer circuit board and improving the film thickness uniformity, 32% by mass or more is more preferable, 34% by mass or more is further preferable, 36% by mass or more is further more preferable, and 38% by mass or more. Is more preferably 40% by mass or more, particularly preferably 42% by mass or more.

In addition, the curable resin composition content rate in a prepreg is defined as follows.

Further, in order to achieve rigidity and thinning of the prepreg, the content ratio of the sheet-like fiber substrate and the inorganic filler in the prepreg (the mass of the sheet-like fiber substrate / the mass of the inorganic filler) is 0.2 to It is preferable to control to 2.5. Furthermore, the content ratio is more preferably 2.3 or less from the viewpoint that the linear thermal expansion coefficient can be efficiently reduced by filling the gaps in the sheet-like fiber base material with many inorganic fillers. 0.1 or less is more preferable, 1.9 or less is still more preferable, 1.7 or less is still more preferable, and 1.5 or less is especially preferable. Moreover, when there are too many inorganic fillers, the melt viscosity of a curable resin composition will be raised and it will become difficult for an inorganic filler to enter into the clearance gap between sheet-like fiber base materials efficiently. 3 or more is more preferable, 0.4 or more is more preferable, and 0.5 or more is still more preferable.

Thus, by controlling the configuration of the prepreg, it is possible to obtain a suitable prepreg with a support for vacuum lamination by heating and pressurizing the inner layer circuit board, and by using such a prepreg with a support. It is possible to provide a method for producing a thin multilayer printed wiring board having sufficient rigidity.

[Vacuum lamination method]
In the step (A), the prepreg with the support is heated and pressed on the inner layer circuit board and vacuum laminated. Here, when the protective film is attached to the prepreg with the support, after the protective film is peeled off, the prepreg surface of the prepreg with the support is faced to the inner layer circuit board and supported by heating and pressing using a vacuum laminator. The prepreg with body is vacuum laminated on the inner circuit board. In addition, from the point of productivity improvement, in the step (A), the prepreg with the support wound in a roll shape is peeled off when the protective film is laminated, and then supplied to the vacuum laminator sequentially and continuously. It is preferable that the prepreg surface of the prepreg with the support is opposed to the inner layer circuit board and heated and pressurized using a vacuum laminator to vacuum laminate the prepreg with the support. Here, the inner layer circuit board refers to a board having a conductor layer having a wiring pattern formed on one side or both sides. When a multilayer printed wiring board is manufactured, an insulating layer and a conductor layer are further formed on the board. An intermediate product to say. Examples of the substrate used for the inner circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The thickness of the inner layer circuit board is preferably 0.05 to 0.9 mm, more preferably 0.05 to 0.7 mm, from the viewpoint of achieving a multilayer printed wiring board having sufficient rigidity and a reduced thickness. 0.1 to 0.5 mm is more preferable, and 0.15 to 0.3 mm is even more preferable.

Examples of the vacuum laminator include a batch type laminator and a roll type laminator, but a batch type laminator is preferable from the viewpoint of improving the smoothness of the obtained insulating layer. Commercially available vacuum laminators include, for example, batch type vacuum press laminator MVLP-500 manufactured by Meiki Seisakusho Co., Ltd., vacuum applicator manufactured by Nichigo Morton Co., Ltd., roll dry coater manufactured by Hitachi Industries, Ltd. Examples include a vacuum laminator manufactured by Hitachi IC Corporation.

Lamination using a vacuum laminator is performed by temporarily attaching a prepreg to an inner layer circuit board by an auto cutter, and the inner layer circuit board on which the prepreg is temporarily attached is conveyed into a vacuum chamber of the vacuum laminator. Can be performed by pressing a metal plate such as a heated SUS end plate from the support side through an elastic material such as heat-resistant rubber (see International Publication No. 2009/35014 pamphlet, etc.).

The heating temperature at the time of lamination is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, still more preferably 90 ° C. or higher, from the viewpoint of improving the adhesion between the prepreg and the inner circuit board and improving smoothness. More preferably, the temperature is higher than or equal to ° C. Also, from the viewpoint of heat resistance of the transport PET used in the laminator apparatus, from the viewpoint of obtaining film thickness uniformity, and from the viewpoint of preventing the curable resin composition from exuding, it is preferably 160 ° C or lower, more preferably 150 ° C or lower. 140 ° C. or lower is more preferable, and 130 ° C. or lower is still more preferable.

The time during lamination (pressing time with a metal plate) is preferably 10 seconds or longer, more preferably 15 seconds or longer, further preferably 20 seconds or longer, and even more preferably 25 seconds or longer, from the viewpoint of sufficiently flowing the resin. . From the viewpoint of improving productivity, it is preferably 300 seconds or shorter, more preferably 250 seconds or shorter, still more preferably 200 seconds or shorter, even more preferably 150 seconds or shorter, even more preferably 100 seconds or shorter, particularly preferably 50 seconds or shorter. .

The vacuum during lamination is preferably 0.001 kPa or more, more preferably 0.003 kPa or more, still more preferably 0.005 kPa or more, and even more preferably 0.007 kPa or more, from the viewpoint of efficiently performing the lamination process. 0.01 kPa or more is particularly preferable. In addition, from the viewpoint of preventing air from entering the insulating layer and suppressing the generation of voids, and from the viewpoint of reducing undulation, it is preferably 0.40 kPa or less, more preferably 0.27 kPa or less, and 0.13 kPa or less. More preferably, 0.11 kPa or less is even more preferable, 0.080 kPa or less is particularly preferable, 0.053 kPa or less is particularly preferable, and 0.035 kPa or less or 0.027 kPa is particularly preferable.
The time to reach the predetermined degree of vacuum (hereinafter referred to as “vacuum arrival time”) is 15 seconds or less, preferably 14 seconds or less, more preferably from the viewpoint of suppressing the generation of voids in the insulating layer. Is 12 seconds or less, more preferably 10 seconds or less, even more preferably 8 seconds or less, and particularly preferably 6 seconds or less. The vacuum arrival time refers to the elapsed time from the time when the vacuum chamber is closed and the degree of vacuum starts to drop until the predetermined vacuum degree is reached in the vacuum laminator.

The pressurization at the time of lamination is preferably 1 kgf / cm ² or more from the viewpoint of flowing the curable resin composition and embedding between the wiring patterns to improve the adhesion with the inner circuit board, and 1.5 kgf / cm ^2. The above is more preferable, 2 kgf / cm ² or more is more preferable, and 3 kgf / cm ² or more is even more preferable. Also, to prevent the oozing of the curable resin composition, from the viewpoint of obtaining a uniform insulating layer having a thickness, preferably 16 kgf / cm ² or less, more preferably 13 kgf / cm ² or less, is 11 kgf / cm ² or less More preferably, 9 kgf / cm ² or less is even more preferable, and 7 kgf / cm ² or less is even more preferable.

Thus, in the present invention, in the step (A), by controlling the configuration of the prepreg and also controlling the vacuum lamination method, the prepreg is used to suppress voids, and the glass transition temperature is high. An insulating layer having a low thermal expansion coefficient and a uniform film thickness can be formed on the inner circuit board. Therefore, according to the method of the present invention, it is possible to produce a multilayer printed wiring board that has a sufficient rigidity and is thinned.
Specifically, a prepreg with a support provided with a prepreg having the above-described specific configuration has a degree of vacuum of 0.001 to 0.40 kPa at the time of lamination, a vacuum arrival time of 15 seconds or less, and a pressure of 1 at the time of lamination. By laminating on the inner circuit board by a specific vacuum laminating method that is ~ 16kgf / cm ² , heating temperature during lamination is 60 ~ 160 ° C, and lamination time is 10 ~ 300 seconds, voids are suppressed and glass transition An insulating layer having a uniform film thickness with a high temperature and a low coefficient of linear thermal expansion can be formed on the inner layer circuit board. As a result, a multilayer printed wiring board having a sufficient rigidity and a thin layer can be obtained. Can be manufactured.

<(B) Process>
(B) A process is a process of thermosetting a prepreg and forming an insulating layer. By performing the step (B) after the step (A), an insulating layer can be formed on the inner layer circuit board. Especially, the heat resistance of the insulating layer of a multilayer printed wiring board and a glass transition temperature can be improved by thermosetting a prepreg using a heating oven to form an insulating layer. Furthermore, by placing the prepreg in a vertical state in a heating oven and thermosetting to form an insulating layer, a large number of sheets can be put into the heating oven at one time. From step (A) to (B) It enables continuous and smooth work on the process, contributing to productivity improvement. As the heating oven, for example, a clean oven (“Clean Oven DE610” manufactured by Yamato Scientific Co., Ltd.) or the like can be used.

[Curing method]
From the viewpoint of preventing thermal decomposition of the curable resin composition, the temperature during thermosetting is preferably 250 ° C. or lower, more preferably 240 ° C. or lower, still more preferably 230 ° C. or lower, even more preferably 220 ° C. or lower, 210 It is particularly preferable that the temperature is not higher than ° C. Further, from the viewpoint of sufficient heat curing of the curable resin composition, 150 ° C. or higher is preferable, 160 ° C. or higher is more preferable, 170 ° C. or higher is further preferable, 180 ° C. or higher is even more preferable, and 190 ° C. or higher is particularly high. preferable.

The time for thermosetting is preferably 300 minutes or less, more preferably 180 minutes or less, still more preferably 120 minutes or less, and even more preferably 110 minutes or less, from the viewpoint of preventing thermal decomposition of the curable resin composition. Particularly preferred are minutes or less. Further, from the viewpoint of sufficiently curing the curable resin composition, it is preferably 30 minutes or longer, more preferably 60 minutes or longer, still more preferably 70 minutes or longer, and even more preferably 80 minutes or longer.

The upper limit value of the linear thermal expansion coefficient of the insulating layer is preferably 15 ppm or less, more preferably less than 15 ppm, still more preferably 13 ppm or less, still more preferably 11 ppm or less, and even more preferably 10 ppm or less, from the viewpoint of improving mountability of chips and the like. More preferably, 9.5 ppm or less is particularly preferred, 9 ppm or less is particularly preferred, and 8.5 ppm or less is particularly preferred. According to the present invention, even an insulating layer having an extremely low linear thermal expansion coefficient of less than 8 ppm can be realized. The lower limit of the linear thermal expansion coefficient is not particularly limited, but is generally 1 ppm or more.

The lower limit of the glass transition temperature of the insulating layer is preferably 181 ° C. or higher, more preferably 183 ° C. or higher, and 185 ° C. from the viewpoint of preventing cracking of the insulating layer and improving the mountability of chips and the like by reducing warpage at high temperatures. The above is more preferable. The upper limit of the glass transition temperature of the insulating layer is not particularly limited, but is generally 270 ° C. or lower.

In the step (B), it is more preferable to employ a method in which the multilayer printed wiring board is fixed with a heat-resistant jig, the prepreg is thermally cured, and the multilayer printed wiring board inside the jig is cut out after curing. Thereby, a multilayer printed wiring board can be made into a smooth state without a wrinkle, and an external appearance can be kept favorable. As a method of fixing with a heat-resistant jig, for example, a method of fixing at least two of the four sides of the multilayer printed wiring board with a heat-resistant jig, a method of hanging by its own weight across the upper two ends of the multilayer printed wiring board, For example, a method of fixing all parts of the multilayer printed wiring board with a width of 5 mm from the four sides by a heat-resistant jig can be mentioned. In addition, the multilayer printed wiring board as used in the (B) process means an inner layer circuit board on which the prepreg is laminated in the (A) process.

<Process (C)>
The production method of the present invention may further include (C) a step of peeling the support (step (C)). As a result, the surface of the insulating layer can be exposed to proceed to another process. The step (C) may be performed before the step (B) or may be performed after the step (B), but is preferably performed after the step (B) from the viewpoint of improving the smoothness of the insulating layer. . When the support is a plastic film, the support can be peeled manually or by mechanical removal with an automatic peeling device. When the support is a metal foil, the support can be peeled and removed by dissolving the metal foil with an etching solution or the like.

<(D) Process>
The manufacturing method of the present invention may further include (D) a step of forming a via hole ((D) step). Thereby, conduction between the layers of the insulating layer can be performed. The step (D) is not particularly limited as long as the object is achieved, and a via hole can be formed by a known method. For example, a mechanical drill or a laser such as a carbon dioxide laser or a YAG laser can be used. The step (D) is preferably performed after the step (B). Moreover, although (D) process may be performed before (C) process and may be performed after (C) process, it is preferable to perform before (C) process. By doing so, the via shape can be kept good.

<(E) Process>
The production method of the present invention may further include (E) a desmear process ((E) process). Thereby, the surface of the insulating layer can be roughened to improve the plating adhesion, and the resin residue in the via hole can be removed. In the step (E), a known method such as a dry method such as plasma treatment or a wet method such as oxidant treatment can be used, but oxidant treatment is preferable. (E) When performing an oxidizing agent process in a process, it is preferable to perform the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralization liquid in this order. Although there is no restriction | limiting in particular as swelling liquid, For example, an alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution. The alkaline solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securigans P (Swelling Dip Securigans SBU) and Swelling Dip Securigans SBU manufactured by Atotech Japan Co., Ltd. be able to. The swelling treatment with the swelling liquid is not particularly limited, but is performed by applying a swelling liquid of 50 to 80 ° C. to the insulating layer surface for 1 to 15 minutes from the viewpoint of improving workability and preventing the resin from being excessively swollen. Is preferred. Although there is no restriction | limiting in particular as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in sodium hydroxide aqueous solution can be mentioned. Roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by subjecting the surface of the insulating layer to an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. Moreover, there is no restriction | limiting in particular as a neutralization liquid, However, An acidic aqueous solution is preferable, As a commercial item, Atotech Japan Co., Ltd. reduction shorysin securigant P (neutralization liquid) is mentioned. For the treatment with the neutralizing solution, a method of applying a neutralizing solution at 30 to 60 ° C. for 5 to 20 minutes to the treated surface that has been roughened with an oxidizing agent solution can be used. The step (E) is preferably performed after the step (C) and the step (D). By doing so, the surface of the insulating layer and the via wall surface can be roughened, and the resin residue in the via can be removed.

<(F) Process>
The manufacturing method of the present invention may further include (F) a step of forming a conductor layer by plating ((F) step). (F) A process can be performed by a well-known method. For example, the conductor layer can be formed by combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. Examples of the conductor used for the conductor layer include copper, nickel, gold, and palladium, and copper is particularly preferable.

In the production method of the present invention, a multilayer printed wiring board can be produced by appropriately repeating the above-described steps. Note that the present invention is a method suitable for build-up, and the outermost solder resist is also part of the build-up, and therefore can be applied.

<Semiconductor device>
A method for manufacturing a semiconductor device of the present invention will be described. A semiconductor device is manufactured by bonding a semiconductor element to the connection electrode portion on the multilayer printed wiring board of the present invention. The mounting method of the semiconductor element is not particularly limited, and examples thereof include wire bonding mounting, flip chip mounting, mounting with an anisotropic conductive film (ACF), mounting with a non-conductive film (NCF), and the like. The multilayer printed wiring board of the present invention has a build-up layer made of a prepreg and is a highly rigid multilayer printed wiring board, has a high mountability of a semiconductor chip, and can be suitably used for a semiconductor device.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In the following description, “part” means “part by mass”.

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

<Measurement and evaluation of linear thermal expansion coefficient>
The prepregs produced in the examples and comparative examples were cut into a size of 500 mm × 500 mm with a cutting machine. A prepreg was placed between two copper foils (MT18Ex manufactured by Mitsui Mining & Smelting Co., Ltd.) having a larger area than the prepreg, and a laminator manufactured by Nichigo Morton Co., Ltd. (2-stage buildup laminator CVP7200) was used. Lamination was performed under the same conditions as the vacuum lamination or vacuum press of each example and comparative example, and the prepreg was thermoset under the same conditions. Thereafter, the copper foil was immersed in an aqueous iron (II) chloride solution (manufactured by Tsurumi Soda Co., Ltd., Baume degree 40) to remove the copper foil, thereby obtaining a cured product sample. The cured product sample was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). . After the sample was mounted on the apparatus, it was measured twice in succession under measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient (ppm) in the temperature range from 25 ° C. to 150 ° C. in the second measurement was calculated. The case where the value of linear thermal expansion coefficient was less than 8 ppm was evaluated as “◎”, 8 ppm or more but less than 12 ppm as “◯”, 12 ppm or more but less than 15 ppm as “Δ”, and 15 ppm or more as “×”.

<Measurement and evaluation of glass transition temperature>
The cured material sample was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a dynamic viscoelasticity measuring apparatus (EXSTAR6000 manufactured by SII Nanotechnology Co., Ltd.). . After mounting the sample on the apparatus, the measurement was performed twice continuously under the measurement conditions of a load of 200 mN and a heating rate of 2 ° C./min. The glass transition temperature (° C.) was calculated from the point at which the slope of the dimensional change signal in the second measurement changed. A glass transition temperature value of 185 ° C. or higher was evaluated as “◯” and less than 185 ° C. was evaluated as “X”.

<Evaluation of film thickness uniformity>
The support was peeled off (removed) from the multilayer printed wiring boards produced in the examples and comparative examples. After that, when the surface of the insulating layer is cut into 200 mm × 200 mm test pieces and the surface state is observed using an optical interference type surface roughness / surface shape measuring device (Wyko NT9300, manufactured by Veeco Japan), the undulation is less than 3 μm. Was evaluated as “◎” when 3 μm or more and less than 5 μm, “◯” when 5 μm or more but less than 7 μm, “Δ” when 7 μm or more but less than 9 μm, and “×” when 9 μm or more. .

<Appearance evaluation>
The support was peeled off (removed) from the multilayer printed wiring boards produced in the examples and comparative examples. Thereafter, the surface of the insulating layer is cut into a 200 mm × 200 mm test piece, and the surface state is observed using a microscope (Microscope VH-5500, manufactured by KEYENCE Co., Ltd.). The evaluation was “◯” for 1 to 3 pieces, “Δ” for 4 to 6 pieces, and “×” for 7 or more pieces.

<Example 1>
(1) Preparation of prepreg with support 20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, DIC Corporation) 25 parts of “HP4710”) and 5 parts of phenoxy resin (“YL7553BH30” manufactured by Japan Epoxy Resin Co., Ltd.) were dissolved in 15 parts of MEK and 15 parts of cyclohexanone with stirring. Thereto, 15 parts of a MEK solution having a solid content of 60% by weight of a triazine skeleton-containing phenol novolak resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, nitrogen content approximately 12% by weight), naphthol-based curing agent (hydroxyl equivalent) 215, 15 parts of MEK solution with a solid content of 60% by weight of “SN-485” manufactured by Tohto Kasei Co., Ltd., solid content of naphthol-based curing agent (hydroxyl equivalent 153, “EXB-9500” manufactured by DIC Corporation) 50 5 parts by weight MEK solution, 10 parts of reactive flame retardant (hydroxyl equivalent 162, “HCA-HQ” manufactured by Sanko Co., Ltd., phosphorus content 9.5%), spherical silica (average particle size 0.5 μm, ( 250 parts by weight of “SOC2” manufactured by Admatechs Co., Ltd., with aminosilane treatment, ethanol with a solid content of 15% by weight of polyvinyl butyral resin (“KS-1” manufactured by Sekisui Chemical Co., Ltd.) Toluene of 1: 1 solution 5 parts were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. The varnish was impregnated into 1067 glass cloth (thickness 33 μm) manufactured by Arisawa Manufacturing Co., Ltd., and dried at 130 ° C. for 5 minutes in a vertical drying furnace to prepare a prepreg. The residual solvent amount of the prepreg is 0.1 to 2% by mass in the curable resin composition not containing glass cloth, the content of the curable resin composition in the prepreg is 42% by mass, the thickness of the prepreg is 48 μm, and the thickness of the prepreg is The thickness of the sheet-like fiber base material when set to 1 was 0.69, and the content ratio of the sheet-like fiber base material and the inorganic filler in the prepreg was 1.8. After that, a prepreg was placed between the release surface of a PET film having a thickness of 38 μm (AL5 manufactured by Lintec Corporation) and a polypropylene film having a thickness of 15 μm, and a laminator manufactured by Nichigo Morton Co., Ltd. (two-stage buildup laminator). CVP7200) was used to wind up into a roll while bonding, and a prepreg with a support wound into a roll was produced.

(2) Production of inner layer circuit board
A wiring pattern is formed on both sides of a glass cloth base epoxy resin double-sided copper-clad laminate [copper foil thickness 18 μm, substrate thickness 0.2 mm, Matsushita Electric Works R1515A], and a microetching agent (MEC A roughening process was performed with CZ8100 manufactured by Co., Ltd. to produce an inner layer circuit board.

(3) Lamination of the prepreg with the support The prepreg with the support is peeled off the protective film, and sequentially supplied to the Nichigo-Morton laminator (2-stage build-up laminator CVP7200) in the above (2). Lamination was performed on both surfaces of the produced inner circuit board. Lamination was carried out for 30 seconds under lamination conditions of a vacuum degree of lamination of 0.05 kPa, a vacuum arrival time of 5 seconds, a pressure of 7 kgf / cm ² , and a temperature of 120 ° C. The evacuation time was 0.5 minutes.

(4) Curing of the curable resin composition The substrate is fixed to all parts having a width of 5 mm from the four sides with a heat-resistant jig, and then the substrate is put into a heating oven in a vertical state at an atmospheric pressure of 210 ° C. A multilayer printed wiring board was produced by thermosetting for 90 minutes.

<Example 2>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 55% by mass, the thickness of the prepreg is 52 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.63. And the content ratio of the inorganic filler was 1.1. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Example 3>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 65% by mass, the thickness of the prepreg is 55 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.6. And the content ratio of the inorganic filler became 0.7. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Example 4>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 75% by mass, the thickness of the prepreg is 63 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.52. And the content ratio of the inorganic filler became 0.4. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Example 5>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 55% by mass, the thickness of the prepreg is 52 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.63. And the content ratio of the inorganic filler was 1.1. And the multilayer printed wiring board was produced like Example 1 except having changed the pressurization at the time of lamination | stacking into 3 kgf / cm < ² >.

<Example 6>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 55% by mass, the thickness of the prepreg is 52 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.63. And the content ratio of the inorganic filler was 1.1. And the multilayer printed wiring board was produced like Example 1 except having changed the pressurization at the time of lamination | stacking into 15 kgf / cm < ² >.

<Example 7>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 55% by mass, the thickness of the prepreg is 52 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.63. And the content ratio of the inorganic filler was 1.1. And the multilayer printed wiring board was produced like Example 1 except having changed the vacuum degree at the time of lamination | stacking to 0.03 kPa.

<Example 8>
Except for the point that the impregnation amount of the resin varnish into the glass cloth was changed, and the 1035 type quartz glass cloth (thickness 32 μm, Q glass fiber) manufactured by Shin-Etsu Quartz Co., Ltd. and IPC standard as the glass cloth, In the same manner as in Example 1, a prepreg with a support was produced. The content of the curable resin composition in the prepreg is 55% by mass, the thickness of the prepreg is 45 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.71. And the content ratio of the inorganic filler was 1.1. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Example 9>
A prepreg with a support was prepared in the same manner as in Example 1 except that the amount of resin varnish impregnated into the glass cloth was changed and copper foil (MT18Ex manufactured by Mitsui Mining & Smelting Co., Ltd.) was used as the support. Produced. The content of the curable resin composition in the prepreg is 55% by mass, the thickness of the prepreg is 52 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.63. And the content ratio of the inorganic filler was 1.1. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Example 10>
20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation) and 25 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4710” manufactured by DIC Corporation) It was heated and dissolved in 15 parts of MEK and 15 parts of cyclohexanone with stirring. Thereto, 15 parts of a MEK solution having a solid content of 60% by weight of a triazine skeleton-containing phenol novolak resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, nitrogen content approximately 12% by weight), naphthol-based curing agent (hydroxyl equivalent) 215, 15 parts of MEK solution with a solid content of 60% by weight of “SN-485” manufactured by Tohto Kasei Co., Ltd., solid content of naphthol-based curing agent (hydroxyl equivalent 153, “EXB-9500” manufactured by DIC Corporation) 50 Mix 5 parts by weight of MEK solution of 5% and 250 parts of MEK slurry solution of 60% by weight solid content of spherical silica (average particle size 0.05μm, “YA050C-MJA” manufactured by Admatechs Co., Ltd.) To obtain a resin varnish. The varnish was impregnated into 1067 glass cloth (thickness 33 μm) manufactured by Arisawa Manufacturing Co., Ltd. and dried at 130 ° C. for 5 minutes in a vertical drying furnace to prepare a prepreg precursor. The thickness of the prepreg precursor was 41 μm. The prepreg precursor was further impregnated into the resin varnish of Example 1, and dried at 130 ° C. for 5 minutes in a vertical drying oven to prepare a prepreg. The final amount of residual solvent of the prepreg is 0.1 to 2% by mass in the curable resin composition not containing glass cloth, the content of the curable resin composition in the prepreg is 55% by mass, the thickness of the prepreg is 52 μm, and the prepreg When the thickness of the sheet-like fiber substrate is 1, the thickness of the sheet-like fiber substrate is 0.63, and the content ratio of the sheet-like fiber substrate and the inorganic filler in the prepreg is 1.0. Thereafter, a multilayer printed wiring board was produced in the same manner as in Example 1.

<Example 11>
20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation), 20 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4710” manufactured by DIC Corporation), 10 parts of a naphthylene ether type epoxy resin (epoxy equivalent 248, “HP6000” manufactured by DIC Corporation) was dissolved in 15 parts of MEK and 15 parts of cyclohexanone with stirring. Thereto, 15 parts of a MEK solution having a solid content of 60% by weight of a triazine skeleton-containing phenol novolak resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, nitrogen content approximately 12% by weight), naphthol-based curing agent (hydroxyl equivalent) 215, 15 parts of MEK solution having a solid content of 60% by weight of “SN-485” manufactured by Toto Kasei Co., Ltd., solid of naphthylene ether type curing agent (hydroxyl equivalent 155, “EXB-6000” manufactured by DIC Corporation) 5 parts by weight of MEK solution of 50% by weight and 250 parts of MEK slurry solution of 60% by weight solid content of spherical silica (average particle size 0.05 μm, “YA050C-MJA” manufactured by Admatechs Co., Ltd.) To uniformly disperse the resin varnish. The varnish was impregnated into 1067 glass cloth (thickness 33 μm) manufactured by Arisawa Manufacturing Co., Ltd., and dried at 130 ° C. for 5 minutes in a vertical drying furnace to prepare a prepreg. The content of the curable resin composition in the prepreg is 55% by mass, the thickness of the prepreg is 52 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.63. And the content ratio of the inorganic filler was 1.1. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Example 12>
A prepreg with a support is produced in the same manner as in Example 1, except that the amount of resin varnish impregnated into the glass cloth is changed and a 1015 glass cloth (thickness 15 μm) manufactured by Arisawa Seisakusho is used as the glass cloth. did. The content of the curable resin composition in the prepreg is 81% by mass, the thickness of the prepreg is 50 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.30. And the content ratio of the inorganic filler became 0.3. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Example 13>
In the same manner as in Example 1, a prepreg with a support was produced. And the multilayer printed wiring board was produced like Example 1 except having made vacuum arrival time into 10 second. That is, the laminate was laminated for 30 seconds under the lamination conditions of 0.05 kPa during lamination, a vacuum arrival time of 10 seconds, a pressure of 7 kgf / cm ² , and a temperature of 120 ° C. The evacuation time was 0.75 minutes.

<Example 14>
In the same manner as in Example 1, a prepreg with a support was produced. And the multilayer printed wiring board was produced like Example 1 except having made vacuum arrival time into 15 second. That is, lamination was performed for 30 seconds under a lamination condition of a vacuum degree of 0.05 kPa at the time of lamination, a vacuum arrival time of 15 seconds, a pressure of 7 kgf / cm ² , and a temperature of 120 ° C. The evacuation time was 0.75 minutes.

<Comparative Example 1>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 65 wt%, the thickness of the prepreg is 55 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is The content ratio with the inorganic filler was 0.7. And the multilayer printed wiring board was produced like Example 1 except having changed the vacuum degree at the time of lamination | stacking to 101.3 kPa.

<Comparative example 2>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 65 wt%, the thickness of the prepreg is 55 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is The content ratio with the inorganic filler was 0.7. And the multilayer printed wiring board was produced like Example 1 except having changed the pressurization at the time of lamination | stacking into 25 kgf / cm < ² >.

<Comparative Example 3>
A prepreg with a support is produced in the same manner as in Example 1, except that the amount of resin varnish impregnated into the glass cloth is changed and a 1015 glass cloth (thickness 15 μm) manufactured by Arisawa Seisakusho is used as the glass cloth. did. The content of the curable resin composition in the prepreg is 90% by mass, the thickness of the prepreg is 70 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.21. And the content ratio of the inorganic filler was 1.1. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Comparative Example 4>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 28 wt%, the thickness of the prepreg is 37 μm, and the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1 is 0.89, and the sheet-like fiber substrate in the prepreg The content ratio with the inorganic filler was 3.4. A multilayer printed wiring board was produced in the same manner as in Example 1.

<Comparative Example 5>
A prepreg with a support was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 55 wt%, the thickness of the prepreg is 52 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the thickness of the sheet-like fiber substrate in the prepreg is 0.63. The content ratio with the inorganic filler was 1.1. And the multilayer printed wiring board was produced like Example 1 except having changed the vacuum degree at the time of lamination | stacking to 0.6 kPa.

<Comparative Example 6>
(1) Production of prepreg with support A prepreg was produced in the same manner as in Example 1 except that the amount of the resin varnish impregnated into the glass cloth was changed. The content of the curable resin composition in the prepreg is 65 wt%, the thickness of the prepreg is 55 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is The content ratio with the inorganic filler was 0.7. Thereafter, a prepreg was placed between the glossy surface of copper foil (MT18Ex manufactured by Mitsui Mining & Smelting Co., Ltd.) and a polypropylene film having a thickness of 15 μm, and a laminator manufactured by Nichigo Morton Co., Ltd. (two-stage buildup laminator CVP7200). Was used to prepare a prepreg with a support that was wound into a roll while being bonded together.
(2) Production of inner layer circuit board An inner layer circuit board was produced in the same manner as in Example 1.
(3) Pressing of prepreg with support and curing of curable resin composition After peeling off the protective film, the prepreg with support was peeled off on both sides of the inner layer circuit board prepared in (2) above by using a vacuum press ( ) Using MNPC-V-750-750-5-200 manufactured by Meiki Seisakusho, the degree of vacuum during pressing is 1 kPa, the pressure is 10 kgf / cm ² , and the heating rate is 3 ° C./min. After the temperature was raised to 115 ° C., the pressure was set to 30 kgf / cm ² , the temperature was raised from 115 ° C. to 230 ° C. at a rate of temperature rise of 3 ° C./min, and maintained for 90 minutes, thereby producing a multilayer printed wiring board. .

<Comparative Example 7>
A prepreg with a support is produced in the same manner as in Example 1, except that the amount of resin varnish impregnated into the glass cloth is changed and a 1015 glass cloth (thickness 15 μm) manufactured by Arisawa Seisakusho is used as the glass cloth. did. The content of the curable resin composition in the prepreg is 90% by mass, the thickness of the prepreg is 70 μm, the thickness of the sheet-like fiber substrate when the thickness of the prepreg is 1, and the sheet-like fiber substrate in the prepreg is 0.21. And the content ratio of the inorganic filler was 1.1. And the multilayer printed wiring board was produced like the comparative example 6. FIG.

<Comparative Example 8>
In the same manner as in Example 1, a prepreg with a support was produced. And the multilayer printed wiring board was produced like Example 1 except having made vacuum arrival time into 20 second. That is, lamination was performed for 30 seconds under a lamination condition of a degree of vacuum at the time of lamination of 0.05 kPa, a vacuum arrival time of 20 seconds, a pressure of 7 kgf / cm ² and a temperature of 120 ° C. The evacuation time was 0.75 minutes.

The measurement results are shown in Tables 1 and 2.

According to Examples 1 to 14, according to the manufacturing method of the present invention, a multilayer printed wiring board having an insulating layer with a uniform film thickness having a high glass transition temperature, a low coefficient of linear thermal expansion, and suppressed generation of voids is obtained. I was able to. It can be seen that it is an excellent effect of the present invention that a multilayer printed wiring board can be produced by employing a specific prepreg and a specific vacuum lamination method. In Comparative Example 1, since pressure was not reduced at the time of lamination, air entered between the prepreg and the inner layer circuit board, resulting in poor appearance. In Comparative Example 2, since the pressurization at the time of lamination was large, a resin ooze (flow) occurred, the film thickness became non-uniform, and the appearance was poor. Since the comparative example 3 had too much curable resin composition content, it became difficult to make a linear thermal expansion coefficient low. Since the comparative example 4 had too little content of curable resin composition, the external appearance became bad. In Comparative Example 5, since the degree of vacuum at the time of lamination was insufficient, air between the prepreg and the inner layer circuit board did not escape sufficiently, resulting in poor appearance. In Comparative Example 6, since lamination and heating are performed using a vacuum press machine, the degree of vacuum is insufficient, the air between the prepreg and the inner circuit board is not sufficiently removed, the appearance is deteriorated, and the glass transition The temperature did not improve. Comparative Example 7 in which the content of the curable resin composition in the prepreg is high and lamination and thermosetting are performed using a vacuum press machine is excellent in film thickness uniformity and appearance after removal of the copper foil, but linear thermal expansion. The result was an insulating layer with a large coefficient and a low glass transition temperature. In Comparative Example 8, since the time to reach the vacuum at the time of lamination was long, the generation of voids was remarkable and the appearance was poor.

According to the present invention, by combining a specific prepreg and a specific vacuum laminating method, a multilayer printed wiring board having an insulating layer having a uniform glass thickness, a high glass transition temperature, a low linear thermal expansion coefficient, and no voids. You can get In addition, electrical products such as semiconductor devices, computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with the multilayer printed wiring board can be provided. It was.

Claims

(A) A step of heating and pressurizing the prepreg with a support to the inner layer circuit board to perform vacuum lamination,
(B) a step of thermosetting the prepreg to form an insulating layer;
A method for producing a multilayer printed wiring board, comprising:
The prepreg contains a curable resin composition and a sheet fiber substrate,
The content of the curable resin composition in the prepreg is 30% by mass or more and 85% by mass or less,
The curable resin composition contains an inorganic filler,
In step (A), the degree of vacuum during lamination is 0.001 to 0.40 kPa, the time to reach vacuum is 15 seconds or less, the pressure during lamination is 1 to 16 kgf / cm 2 , and the heating temperature during lamination is 60 to A method for producing a multilayer printed wiring board, characterized in that the lamination time is 10 to 300 seconds at 160 ° C.
The method for producing a multilayer printed wiring board according to claim 1, wherein the thickness of the sheet-like fiber base material is 0.25 to 0.88 when the thickness of the prepreg is 1.
The content ratio of the sheet-like fiber substrate and the inorganic filler in the prepreg (the mass of the sheet-like fiber substrate / the mass of the inorganic filler) is 0.2 to 2.5. Or the manufacturing method of the multilayer printed wiring board of 2.
The sheet-like fiber base material contains at least one selected from the group consisting of glass cloth, glass nonwoven fabric, organic woven fabric, and organic nonwoven fabric, according to any one of claims 1 to 3. A method for producing a multilayer printed wiring board.
The multilayer according to any one of claims 1 to 3, wherein the sheet-like fiber base material contains at least one selected from the group consisting of E glass fiber, S glass fiber, and Q glass fiber. Manufacturing method of printed wiring board.
The method for producing a multilayer printed wiring board according to any one of claims 1 to 5, wherein the inorganic filler has an average particle diameter of 0.01 to 2 µm.
7. The method for producing a multilayer printed wiring board according to claim 1, wherein the inorganic filler has an average particle diameter of 0.01 to 0.4 μm.
The content of the inorganic filler is 40 to 85% by mass when the nonvolatile component in the curable resin composition is 100% by mass. Manufacturing method for multilayer printed wiring boards.
The content of the inorganic filler is 60 to 85% by mass when the nonvolatile component in the curable resin composition is 100% by mass. Manufacturing method for multilayer printed wiring boards.
In the step (A),
When the protective film is attached to the prepreg with the support wound in a roll shape, the protective film is peeled off and sequentially supplied to the vacuum laminator, and the prepreg surface of the prepreg with the support faces the inner circuit board. The method for producing a multilayer printed wiring board according to any one of claims 1 to 9, wherein the prepreg with a support is vacuum laminated on the inner circuit board by heating and pressurizing using a vacuum laminator.
In the step (B),
The method for producing a multilayer printed wiring board according to any one of claims 1 to 10, wherein the temperature during thermosetting is 150 to 250 ° C and the time during thermosetting is 30 to 300 minutes.
In the step (B),
The method for producing a multilayer printed wiring board according to any one of claims 1 to 11, wherein the insulating layer is formed by thermally curing the prepreg using a heating oven.
In the step (B),
The method for producing a multilayer printed wiring board according to any one of claims 1 to 12, wherein the prepreg is arranged in a vertical state in a heating oven and thermally cured to form an insulating layer.
In the step (B),
The multilayer printed wiring board according to any one of claims 1 to 13, wherein the multilayer printed wiring board is fixed with a heat-resistant jig, the prepreg is thermally cured, and the multilayer printed wiring board inside the jig is cut out after the curing. Manufacturing method of printed wiring board.
The method for producing a multilayer printed wiring board according to any one of claims 1 to 14, wherein a linear thermal expansion coefficient of the insulating layer is 15 ppm or less.
16. The method for producing a multilayer printed wiring board according to claim 1, wherein the insulating layer has a glass transition temperature of 181 ° C. or higher.
The method for producing a multilayer printed wiring board according to any one of claims 1 to 16, further comprising (C) a step of peeling the support.
The method for producing a multilayer printed wiring board according to any one of claims 1 to 17, further comprising (D) a step of forming a via hole.
The method for producing a multilayer printed wiring board according to any one of claims 1 to 18, further comprising (E) a desmear process.
The method for manufacturing a multilayer printed wiring board according to any one of claims 1 to 19, further comprising (F) a step of forming a conductor layer by plating.
A semiconductor device comprising a multilayer printed wiring board obtained by the manufacturing method according to any one of claims 1 to 20.