JP2018101703A - Method for manufacturing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a printed wiring board in which the warp is reduced and the delamination is suppressed.SOLUTION: A method for manufacturing a printed wiring board comprises the steps of: (A) preparing an insulative resin film including a support body and a resin composition layer provided on the support body and formed from a resin composition containing a cyanate ester resin; (B) putting the insulative resin film on an internal layer substrate of 10 ppm or less in thermal expansion coefficient so that the resin composition layer is joined to the internal layer substrate; (C) thermally curing the resin composition layer to form an insulator layer having a glass transition temperature of T1(°C); and (E) heating the insulator layer at T2(°C) so as to meet the following general expression (1): 5°C≤T1-T2≤50°C (1).SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a printed wiring board.

  As a manufacturing technique of a multilayer printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner substrate is known. The insulating layer is generally formed by curing a resin composition.

  For example, Patent Document 1 discloses that an insulating layer in a printed wiring board is formed using a resin composition containing a cyanate ester resin, a specific epoxy resin, and an active ester curing agent. It is described that both a low roughness and a high peel strength of a conductor layer formed by plating are achieved, and a low thermal expansion coefficient is achieved.

JP 2011-144361 A

  In recent years, miniaturization and high density of wiring have been demanded in printed wiring boards due to the need for miniaturization of electronic devices and electronic components. As the wiring becomes finer and higher in density, it is more important to reduce the warpage of the inner layer substrate, and an inner layer substrate having a low coefficient of thermal expansion (CTE) is required to reduce the warpage.

  Since a resin composition containing a cyanate ester resin as described in Patent Document 1 is excellent in heat resistance, it is often used for the formation of an insulating layer. It has been found that delamination tends to occur and delamination tends to occur between the inner layer substrate and the insulating layer or between the insulating layer and the conductor layer.

  The subject of this invention is providing the manufacturing method of the printed wiring board which can suppress reduction of curvature and delamination even if an insulating layer is formed using the resin composition containing cyanate ester resin.

  As a result of investigations by the present inventors, in forming an insulating layer using a resin composition containing a cyanate ester resin, after forming the insulating layer by thermosetting, further heating the insulating layer under specific conditions (annealing treatment) As a result, it has been found that both reduction of warpage and suppression of delamination can be achieved, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) A step of preparing an insulating resin film including a support and a resin composition layer formed on the support and formed from a resin composition including a cyanate ester resin;
(B) A step of laminating an insulating resin film on an inner layer substrate having a coefficient of thermal expansion of 10 ppm or less so that the resin composition layer is bonded to the inner layer substrate;
(C) a step of thermosetting the resin composition layer to form an insulating layer having a glass transition temperature of T1 (° C.);
(E) The manufacturing method of a printed wiring board including the process of heating an insulating layer by T2 (degreeC) so that the following general formula (1) may be satisfy | filled.
5 ° C ≦ T1-T2 ≦ 50 ° C (1)
[2] The method for manufacturing a printed wiring board according to [1], including a step (D) of cooling the insulating layer to room temperature before the step (E).
[3] The method for producing a printed wiring board according to [1] or [2], wherein in the step (E), the insulating layer is heated at T2 (° C.) for 5 to 90 minutes.
[4] The process for producing a printed wiring board according to any one of [1] to [3], wherein in the step (C), the glass transition temperature T1 (° C.) of the insulating layer satisfies 100 ° C. ≦ T1 ≦ 200 ° C. .
[5] The method for manufacturing a printed wiring board according to any one of [1] to [4], including a step of roughening the insulating layer (G) after the step (E).
[6] The method for manufacturing a printed wiring board according to [5], further including (H) a step of forming a conductor layer on the surface of the insulating layer after the step (G).
[7] The method for manufacturing a printed wiring board according to any one of [1] to [6], wherein the insulating layer has a thickness of 100 μm or less.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the printed wiring board which suppressed curvature reduction and delamination can be provided.

[Insulating resin film]
Before describing the method for manufacturing a printed wiring board of the present invention in detail, the “insulating resin film” used in the method for manufacturing a printed wiring board of the present invention will be described.

  The insulating resin film includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from a resin composition including a cyanate ester resin. Hereinafter, the resin composition layer and the support that the insulating resin film has will be described.

(Resin composition layer)
The resin composition used for a resin composition layer will not be specifically limited if it is a resin composition containing cyanate ester resin, For example, the composition containing cyanate ester resin and curable resin is mentioned. As curable resin, arbitrary curable resin used when forming the insulating layer of a printed wiring board can be used, and an epoxy resin is especially preferable. Accordingly, in one embodiment, the resin composition includes a cyanate ester resin and an epoxy resin. The resin composition may further contain additives such as an inorganic filler, a thermoplastic resin, a curing agent (excluding cyanate ester resin), a curing accelerator, a flame retardant, and an organic filler, as necessary. Hereinafter, each component contained in the resin composition will be described in detail.

-Cyanate ester resin-
The resin composition includes a cyanate ester resin. Examples of the cyanate ester resins include novolak-type cyanate ester resins such as phenol novolak type and alkylphenol novolak type; dicyclopentadiene type cyanate ester resins; bisphenol type cyanate ester resins such as bisphenol A type, bisphenol F type, and bisphenol S type, And a prepolymer in which these are partially triazines. You may use these 1 type or in combination of 2 or more types.

  Specific examples of the cyanate ester resin 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-3,5 A bifunctional cyanate resin such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, Phenol novolac, black Tetrazole novolac, polyfunctional cyanate resin derived from dicyclopentadiene structure-containing phenol resin, these cyanate resins and partially triazine of prepolymer.

  A commercially available product may be used as the cyanate ester resin. For example, a phenol novolac type polyfunctional cyanate ester resin represented by the following formula (A) (Lonza Japan, PT30, cyanate equivalent 124), and the following formula (B): Prepolymer (Lonza Japan Co., Ltd., BA230, cyanate equivalent 232) in which a part or all of the bisphenol A dicyanate represented is triazine is formed, containing a dicyclopentadiene structure represented by the following formula (C) Examples include cyanate ester resins (Lonza Japan, DT-4000, DT-7000).

［式（Ａ）中、ｎは平均値としての任意の数を表す。］
式（Ａ）中のｎは０〜２０を表すことが好ましい。

[In formula (A), n represents an arbitrary number as an average value. ]
N in the formula (A) preferably represents 0 to 20.

［式（Ｃ）中、ｎは平均値としての任意の数を表す。］
式（Ｃ）中のｎは０〜５を表すことが好ましい。

[In formula (C), n represents an arbitrary number as an average value. ]
N in Formula (C) preferably represents 0 to 5.

  Although the weight average molecular weight of cyanate ester resin is not specifically limited, Preferably it is 500-4500, More preferably, it is 600-3000. Here, the weight average molecular weight of the cyanate ester resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  The content of the cyanate ester resin in the resin composition is not particularly limited, but from the viewpoint of improving heat resistance, when the nonvolatile component in the resin composition is 100% by mass, 30% by mass or less. Is preferable, 25 mass% or less is more preferable, and 20 mass% or less is still more preferable. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further more preferably 5% by mass or more from the viewpoint of preventing a decrease in heat resistance, preventing an increase in thermal expansion coefficient and preventing an increase in dielectric loss tangent. Preferably, 10% by mass or more is even more preferable.

-Epoxy resin-
In one embodiment, the resin composition may contain an epoxy resin. Examples of the epoxy resin include fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; Dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolac type epoxy resin; phenol novolac type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy Fatty; Epoxy resin having butadiene structure; Alicyclic epoxy resin; Heterocyclic epoxy resin; Spiro ring-containing epoxy resin; Cyclohexane dimethanol type epoxy resin; Naphthylene ether type epoxy resin; Trimethylol type epoxy resin; Type epoxy resin, phosphorus-containing epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, the epoxy resin has excellent flexibility and the breaking strength of the cured product is improved.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (bisphenol A) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin and bisphenol F type epoxy resin), “YD-8125G” (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation , Daicel "Celoxide 2021P" (an alicyclic epoxy resin having an ester skeleton), "PB-3600" (an epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1, 4) manufactured by Nippon Steel Chemical Co., Ltd. -Glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "E-7432", "E-7632" (perfluoroalkyl type epoxy resin) manufactured by Daikin Industries, Ltd., and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (manufactured by DIC) Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311 ”,“ EXA-7311-G3 ”,“ EXA-7311-G4 ”,“ EXA-7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(manufactured by Nippon Kayaku Co., Ltd.) Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “PG” manufactured by Osaka Gas Chemical Co., Ltd. -100 "," CG-500 "," YL7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation," jER1010 "manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin)," jER1031S "(tetraphenyl) Ethane type epoxy tree ) "YL7760" (bisphenol AF type epoxy resin), Nippon Steel Sumitomo Metal Chemical Co. "TX0712-EK75" (phosphorus-containing epoxy resin) and the like.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is provided when used in the form of an insulating resin film, ii) used in the form of an insulating resin film In this case, sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product of the resin composition layer having a sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:10 by mass ratio. Is more preferable, and the range of 1: 0.3 to 1: 3 is more preferable.

  The content of the epoxy resin in the resin composition is preferably 5% by mass when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good tensile fracture strength and insulation reliability. As mentioned above, More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By being in this range, the crosslinked density of the cured product of the resin composition layer is sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

-Inorganic filler-
In one embodiment, the resin composition may contain an inorganic filler. The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.1 micrometer or more, More preferably, it is 0.3 micrometer or more. Examples of commercially available inorganic fillers having such an average particle diameter include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs, and “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd. ”,“ Silfil NSS-3N ”,“ Silfil NSS-4N ”,“ Silfil NSS-5N ”manufactured by Tokuyama Corporation,“ SO-C2 ”,“ SO-C1 ”manufactured by Admatechs, and the like.

  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 methyl ethyl ketone by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring device, “LA-500” manufactured by Horiba, Ltd., “SALD-2200” manufactured by Shimadzu Corporation, etc. can be used.

  Inorganic fillers are fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, and silane-based cups that are fluorine compounds from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as a ring agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent, and more preferably treated with a fluorine-containing silane coupling agent. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-” manufactured by Shin-Etsu Chemical Co., Ltd. 7103 "(3,3,3-trifluoropropyltrimethoxysilane) and the like.

  The degree of the surface treatment with the surface treatment agent is surface-treated with 0.2 to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the inorganic filler from the viewpoint of improving dispersibility of the inorganic filler. It is preferable that the surface treatment is performed at 0.2 to 3 parts by mass, and the surface treatment is preferably performed at 0.3 to 2 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of suppressing the increase in melt viscosity of the resin varnish and the sheet form. preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  From the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion, the content of the inorganic filler in the resin composition is preferably 30% by mass or more, more preferably, when the nonvolatile component in the resin composition is 100% by mass. It is 35% by mass or more, more preferably 40% by mass or more. From the viewpoint of suppressing delamination of the insulating layer, the upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.

-Curing accelerator-
In one embodiment, the resin composition may contain a curing accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5,4,0) -undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation and “jERcure P200H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass to 3% by mass when the nonvolatile component in the resin composition is 100% by mass. 01 mass%-3 mass% are more preferable, and 0.01 mass%-1 mass% are still more preferable.

-Curing agent (except cyanate ester resin)-
In one embodiment, the resin composition may contain a curing agent. However, the curing agent here does not include a cyanate ester resin. As the curing agent, a compound having a function of curing an epoxy resin can be used. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a carbodiimide curing agent, and the like. Is mentioned. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Co., Ltd. “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like manufactured by DIC.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally 1 molecule of ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are carried out. A compound having two or more thereof is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "(manufactured by DIC)," EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure, and" DC808 "as an active ester compound containing an acetylated product of phenol novolac ( Mitsubishi Chemical Co., Ltd.), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylated product of phenol novolac, "YLH1026" as an active ester-based curing agent is benzoyl product of E Nord novolac (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and the like.

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

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 are more preferable, and 1: 0.02 to 1: 1 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By making the quantity ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a resin composition layer improves more.

  When the resin composition contains a curing agent, the content of the curing agent is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably when the nonvolatile component in the resin composition is 100% by mass. Is 15% by mass or less. The lower limit is not particularly limited but is preferably 2% by mass or more.

-Thermoplastic resin-
In one embodiment, the resin composition may contain a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins, and phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The polystyrene-converted weight average molecular weight of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 40,000 or more. Although an upper limit is not specifically limited, Preferably it is 70,000 or less, More preferably, it is 60,000 or less. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-converted weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K- manufactured by Showa Denko KK as a column. 804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as the mobile phase.

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

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, “Electrical butyral 6000-EP”, and Sekisui. Examples include ESREC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industries.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyamideimide resin include “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin also include modified polyamide-imides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers.

  Of these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in a preferred embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Among these, as the thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable. By using a phenoxy resin having a weight average molecular weight of 40,000 or more, the wiring circuit can be miniaturized.

  When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.05% by mass to 5% by mass, more preferably 100% by mass when the nonvolatile component in the resin composition is 100% by mass. It is 0.1 mass%-4 mass%, More preferably, it is 0.15 mass%-3 mass%.

-Organic filler-
In one embodiment, the resin composition may contain an organic filler. By containing an organic filler, the tensile fracture strength of the cured product of the resin composition layer of the insulating resin film can be improved. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

  As the rubber particles, commercially available products may be used, and examples thereof include “EXL2655” manufactured by Dow Chemical Japan, “AC3401N” and “AC3816N” manufactured by Aika Industry.

  When the resin composition contains an organic filler, the content of the organic filler is preferably 1% by mass to 10% by mass and preferably 2% by mass to 5% when the nonvolatile component in the resin composition is 100% by mass. The mass% is more preferable.

-Flame retardant-
In one embodiment, the resin composition may contain a flame retardant. 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. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, such as “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd., and the like. As the flame retardant, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  When the resin composition contains a flame retardant, the content of the flame retardant is preferably 0.5% by mass to 20% by mass, and 0.5% by mass when the nonvolatile component in the resin composition is 100% by mass. -15% by mass is more preferable, and 0.5% by mass to 10% by mass is more preferable.

-Optional additives-
In one embodiment, the resin composition may further contain other additives as necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, and organic cobalt compounds. And organic additives such as thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and color additives.

  The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less or 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

(Support)
Examples of the support used for the insulating resin film include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to mat treatment, corona treatment, and antistatic treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. “AL-5”, “AL-7”, “Lumirror T60” manufactured by Toray Industries, Inc., “Purex” manufactured by Teijin Ltd., “Unipeel” manufactured by Unitika, and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

[Method of manufacturing printed wiring board]
The method for producing a printed wiring board according to the present invention includes:
(A) A step of preparing an insulating resin film including a support and a resin composition layer formed on the support and formed from a resin composition including a cyanate ester resin;
(B) A step of laminating an insulating resin film on an inner layer substrate having a coefficient of thermal expansion of 10 ppm or less so that the resin composition layer is bonded to the inner layer substrate;
(C) a step of thermosetting the resin composition layer to form an insulating layer having a glass transition temperature of T1 (° C.);
(E) A step of heating the insulating layer at T2 (° C.) so as to satisfy the following general formula (1).
5 ° C ≦ T1-T2 ≦ 50 ° C (1)

  Moreover, the manufacturing method of the printed wiring board of this invention may include the process of cooling (D) an insulating layer to room temperature before a (E) process as needed.

  Hereinafter, each process in the manufacturing method of the printed wiring board of this invention is demonstrated.

<(A) Process>
In the step (A), an insulating resin film including a support and a resin composition layer formed on the support and formed from a resin composition including a cyanate ester resin is prepared. The insulating resin film is as described in the above [Insulating resin film].

  The insulating resin film is prepared, for example, by preparing a resin varnish in which a resin composition containing a cyanate ester resin is dissolved in an organic solvent, and applying the resin varnish on a support using a coating device such as a die coater, followed by drying. It can manufacture by making it form a resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  In the insulating resin film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The insulating resin film can be wound and stored in a roll shape. When the insulating resin film has a protective film, it can be used by peeling off the protective film.

<(B) Process>
In this step (B), an insulating resin film is laminated on the inner layer substrate having a thermal expansion coefficient of 10 ppm or less so that the resin composition layer is bonded to the inner layer substrate.

  An inner layer board | substrate is a member used as the board | substrate of a printed wiring board, For example, a glass epoxy board | substrate, a metal board | substrate, a polyester board | substrate, a polyimide board | substrate, a BT resin board | substrate, a thermosetting polyphenylene ether board | substrate etc. are mentioned. Moreover, this board | substrate may have a conductor layer in the single side | surface or both surfaces, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an “inner layer circuit board”. Further, when the printed wiring board is manufactured, an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the “inner layer substrate” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component can be used.

  By using an inner layer substrate having a coefficient of thermal expansion of 10 ppm or less, warpage can be reduced and delamination can be suppressed. The coefficient of thermal expansion of the inner layer substrate is 10 ppm or less, preferably 9 ppm or less, more preferably 8 ppm or less, and even more preferably 7 ppm. The lower limit is not particularly limited, but may be 0.1 ppm or more. The coefficient of thermal expansion of the inner layer substrate can be measured according to the method described in [Measurement of coefficient of thermal expansion (CTE) of inner layer substrate] described later.

  An insulating resin film is laminated on the inner layer substrate so that the resin composition layer is bonded to the inner layer substrate having a coefficient of thermal expansion of 10 ppm or less. In one embodiment, the inner layer substrate and the insulating resin film can be laminated by, for example, thermocompression bonding the insulating resin film to the inner layer substrate from the support side. Examples of the member that heat-presses the insulating resin film to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the thermocompression bonding member directly on the insulating resin film but to press it through an elastic material such as heat-resistant rubber so that the insulating resin film sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the insulating resin film may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After the lamination, the laminated insulating resin film may be smoothed by pressing the thermocompression bonding member from the support side under normal pressure (under atmospheric pressure), for example. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

<Process (C)>
In the step (C), the resin composition layer is thermally cured to form an insulating layer having a glass transition temperature of T1 (° C.).

  The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably in the range of 170 ° C to 200 ° C.) and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

  Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  The glass transition temperature T1 (° C.) of the insulating layer after thermosetting the resin composition layer is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 120 ° C., 130 ° C., 140 ° C., or 150. It is above ℃. Although an upper limit is not specifically limited, Preferably it is 200 degrees C or less, More preferably, it is 190 degrees C or less, More preferably, it is 180 degrees C or less. By setting the glass transition temperature T1 of the insulating layer within the above range, warpage can be reduced and delamination can be suppressed.

  In general, the thinner the insulating layer, the easier the peeling of the insulating layer tends to occur, and it has been difficult for the conventional technique to suppress the peeling. From the viewpoint of making it possible to suppress such peeling, which has been difficult to solve, and effectively utilizing the effects of the present invention, the thinner the insulating layer, the better. The specific thickness of the insulating layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less or 40 μm or less. Although the minimum of the thickness of an insulating layer is not specifically limited, Usually, 1 micrometer or more, 5 micrometers or more, 10 micrometers or more etc. can be used.

<(D) Process>
In one embodiment, the method may include (D) cooling the insulating layer to room temperature. The step (D) is preferably performed between the step (C) and the step (E), that is, before the step (E). By performing the step (D), the relaxation of the stress of the insulating layer in the step (E) can effectively suppress the residual stress in the insulating layer, and the delamination can be further suppressed. Here, room temperature usually represents 10 to 30 ° C.

  The method for cooling is not particularly limited, and the insulating layer may be allowed to cool or the insulating layer may be forcibly cooled. When the insulating layer is forcibly cooled, it may be cooled by various known methods, for example, a method of blowing cool air to the insulating layer, a method of pressing the insulating layer against a cooled roll, and the like.

<(E) Process>
In this step (E), the insulating layer is heated at T2 (° C.) so as to satisfy the following general formula (1). That is, the insulating layer is annealed at a temperature satisfying the general formula (1), which is lower than the thermosetting temperature in the step (C). (E) By performing a process, the stress of an insulating layer can be relieved, As a result, curvature can be reduced and delamination can be suppressed.
5 ° C ≦ T1-T2 ≦ 50 ° C (1)

  As described above, conventionally, when an insulating layer is formed using a resin composition containing a cyanate ester resin, there has been a problem that delamination is likely to occur. By heating the insulating layer at a temperature lower than the glass transition temperature Tg of the insulating layer so as to satisfy (1), the stress in the insulating layer is relaxed, thereby reducing warpage and suppressing delamination. Can do.

  Although it will not specifically limit if it adjusts so that General formula (1) may be satisfy | filled as heating temperature T2 (degreeC), Preferably it is 95 degreeC or more, More preferably, it is 105 degreeC or more, More preferably, it is 115 degreeC, 125 degreeC or more. . An upper limit becomes like this. Preferably it is 150 degrees C or less, More preferably, it is 140 degrees C or less, More preferably, it is 130 degrees C or less.

The heating temperature T2 (° C.) of the insulating layer in the step (E) satisfies the following general formula (1), preferably satisfies the following general formula (2), and more preferably satisfies the following general formula (3). . By heating the insulating layer at T2 (° C.) so that T1-T2 satisfies the general formula (1), warpage can be reduced and delamination can be suppressed.
5 ° C ≦ T1-T2 ≦ 50 ° C (1)
10 ° C ≦ T1-T2 ≦ 45 ° C (2)
15 ° C. ≦ T1-T2 ≦ 40 ° C. (3)

  In the step (E), it is preferable to hold at T2 (° C.) for a predetermined time from the viewpoint of relaxing the stress of the insulating layer. The holding time of T2 (° C.) is preferably 5 to 90 minutes, preferably 15 to 70 minutes, and preferably 20 to 40 minutes.

  The support is between step (B) and step (C), between step (C) and step (D), between step (D) and step (E), or in step (E). It may be removed later.

  The support can be removed by any suitable method known in the art, or mechanically removed by an automatic peeling device. By removing the support, the surface of the formed insulating layer is exposed.

<(F) Process thru | or (H) Process>
When manufacturing a printed wiring board, after the step (E), (F) a step of drilling the insulating layer, (G) a step of roughening the insulating layer, and (H) forming a conductor layer on the surface of the insulating layer. You may further implement the process to do. These steps (F) to (H) may be performed according to various methods known to those skilled in the art, which are used for manufacturing printed wiring boards.

  Step (F) is a step of making a hole in the insulating layer, whereby via holes and through holes can be formed in the insulating layer. The step of drilling can be performed using, for example, a drill, laser (carbon dioxide laser, YAG laser, etc.), plasma, or the like.

  (G) A process is a process of roughening an insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are normally used when forming an insulating layer of a printed wiring board can be employed. (G) A process can be made into the process of carrying out the roughening process of the insulating layer by implementing 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, for example. The swelling liquid is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of the commercially available swelling liquid include “Swelling Dip Securigans P”, “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution / Securigans P” manufactured by Atotech Japan. The treatment with the neutralizing liquid can be performed by immersing the treated surface, which has been subjected to the roughening treatment with the oxidizing agent solution, in a neutralizing liquid at 30 ° C. to 80 ° C. for 5 to 30 minutes.

  Step (H) is a step of forming a conductor layer on the surface of the insulating layer.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of ease of formation of the conductor layer, cost, ease of pattern processing, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy, Copper / nickel alloy, alloy layer of copper / titanium alloy is preferable, single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or alloy layer of nickel / chromium alloy is more preferable, copper The single metal layer is more preferable.

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, it is generally 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  The conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  From the viewpoint of reducing warpage, the remaining copper ratio of the conductor layer is preferably 35 to 85%, more preferably 45 to 75%, and still more preferably 55 to 65%.

  The printed wiring board obtained by the manufacturing method of the present invention exhibits good warpage behavior because warpage is reduced. In one embodiment, the warping behavior is less than 40 μm. The warpage behavior can be measured according to the method described in [Evaluation of warpage behavior] described later.

The printed wiring board obtained by the manufacturing method of the present invention has an excellent effect that delamination between the conductor layer (or wiring layer) and the insulating layer is suppressed. The area where delamination occurs is preferably less than 10%, more preferably 5% or less, and even more preferably 1% or less with respect to the substrate area of 20.25 cm ² . The delamination can be measured according to the method described in [Evaluation of delamination] described later.

[Semiconductor device]
A semiconductor device including such a printed wiring board can be manufactured using the printed wiring board obtained by the manufacturing method of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In the following, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

[Example 1]
(Production of resin varnish)
20 parts by mass of a naphthylene ether type epoxy resin (epoxy equivalent 277, "EXA-7311" manufactured by DIC), 15 parts by mass of liquid bisphenol F type epoxy resin (epoxy equivalent 169, "YL983U" manufactured by Japan Epoxy Resin), phosphorus Containing epoxy resin (“TX0712-EK75” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., MEK solution having a phosphorus content of 2.6% and an epoxy equivalent of about 355 with a nonvolatile content of 75% by mass), 10 parts by mass, a phenoxy resin (weight average molecular weight 38000, Mitsubishi 10 parts by mass of MEK 10 parts by mass, cyclohexanone 5 parts by mass, solvent naphtha 20 parts by mass “YX6954” manufactured by Kagaku Co., Ltd., 10 parts by mass of methyl ethyl ketone (hereinafter abbreviated as “MEK”) having a nonvolatile content of 30% by mass and cyclohexanone The solution was heated and dissolved with stirring. After cooling to room temperature, 20 parts by mass of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan, cyanate equivalent of about 232, non-volatile content of 75% by mass MEK solution), phenol novolac type polyfunctional cyanate ester resin (Lonza Japan “PT30”, cyanate equivalent of about 124, MEK solution with non-volatile content of 80% by mass) Agitated and mixed with 10 parts by mass, and an adduct of an imidazole compound and an epoxy resin as a curing accelerator (manufactured by Mitsubishi Chemical Corporation “ jERcure P200H50 ", propylene glycol monomethyl ether solution having a nonvolatile content of 50% by mass), 0.4 parts by mass, zinc naphthenate (II) mineral spirit solution (manufactured by Wako Pure Chemical Industries, Ltd., containing 8% zinc) 3 parts by mass of solution and spherical silica (Adma 75 parts by mass of “SOC2” manufactured by Tex Co., Ltd., surface-treated with aminosilane (average particle size 0.5 μm) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin composition varnish (resin varnish) .

(Manufacture of insulating resin film)
The prepared resin varnish is uniformly applied on a PET film (thickness 38 μm) with a die coater so that the thickness after drying is 25 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes. Thus, an insulating resin film was obtained.

(Lamination of insulating resin film)
The obtained insulating resin film was laminated on both surfaces of an inner layer circuit board (“MCL-E705G” manufactured by Hitachi Chemical Co., Ltd., thickness of conductor layer: 35 μm, total thickness: 0.4 mm, remaining copper ratio: 60%). This laminate uses a vacuum pressurization type laminator MVLP-500 manufactured by Meiki Seisakusho Co., Ltd., and is vacuum-sucked at a temperature of 100 ° C. for 30 seconds, and then on the PET film under the conditions of a temperature of 100 ° C. and a pressure of 7.0 kg / cm ^2. Lamination was performed by pressing through heat resistant rubber for 30 seconds. Next, pressing was performed for 60 seconds under conditions of a temperature of 100 ° C. and a pressure of 5.5 kg / cm ² using an SUS end plate under atmospheric pressure.

(Thermosetting of insulating resin film)
The PET film is peeled off from the laminated insulating resin film, and the resin composition layer of the insulating resin film is thermally cured under a curing condition of 180 ° C. for 30 minutes using a hot air circulating furnace, so that Tg is 160 ° C. (T1 = 160 ° C.). Next, the substrate was cooled to room temperature (25 ° C.). Immediately after cooling to room temperature, annealing was performed at 130 ° C. (T2 = 130 ° C.) under annealing conditions for 30 minutes. Thereby, the laminated board in which the insulating layer was formed on both surfaces of the inner circuit board was obtained.

(Roughening treatment)
The surface of the insulating layer is immersed in a swelling liquid, Swelling Dip Securigans P (Swelling Dip Securigans P) at 80 ° C. for 10 minutes, and then an concentrate manufactured by Atotech Japan. -It immersed in compact CP for 10 minutes at 80 degreeC, and was finally immersed in the reduction solution securigant P made from Atotech Japan for 5 minutes as a neutralization liquid at 40 degreeC. Thereafter, it was dried at 80 ° C. for 30 minutes.

(Formation of conductor layer by plating)
The roughened laminate was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing the plating seed layer by heating at 150 ° C. for 30 minutes, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 ± 5 μm. Next, the conductor layer was annealed at 180 ° C. for 60 minutes to produce a multilayer printed wiring board.

[Example 2]
In Example 1, the inner layer circuit board was not cooled to room temperature after the insulating resin film was thermally cured before the annealing treatment. Except for the above, a multilayer printed wiring board was obtained in the same manner as in Example 1.

[Example 3]
In Example 1, an inner layer circuit board (“MCL-E705G” manufactured by Hitachi Chemical Co., Ltd., a conductor layer thickness of 35 μm, a total thickness of 0.4 mm) is used as an inner layer circuit board (“HL832NSF-LCA” manufactured by Mitsubishi Gas Chemical Company, Inc.) The thickness of the layer was changed to 35 μm (total thickness: 0.4 mm). Except for the above, a multilayer printed wiring board was obtained in the same manner as in Example 1.

[Example 4]
In Example 1, the annealing process performed at 130 ° C. under the annealing condition for 30 minutes was changed to the annealing process performed at 130 ° C. under the annealing condition for 15 minutes. Except for the above, a multilayer printed wiring board was obtained in the same manner as in Example 1.

[Example 5]
In Example 1, the annealing process performed at 130 ° C. under the annealing condition for 30 minutes was changed to the annealing process performed at 130 ° C. under the annealing condition for 60 minutes. Except for the above, a multilayer printed wiring board was obtained in the same manner as in Example 1.

[Comparative Example 1]
In Example 1, the annealing process performed at 130 ° C. under the annealing condition for 30 minutes was changed to the annealing process performed at 180 ° C. under the annealing condition for 30 minutes. Except for the above, a multilayer printed wiring board was obtained in the same manner as in Example 1.

[Comparative Example 2]
In Example 1, the annealing process performed at 130 ° C. under the annealing condition for 30 minutes was changed to the annealing process performed at 100 ° C. under the annealing condition for 30 minutes. Except for the above, a multilayer printed wiring board was obtained in the same manner as in Example 1.

[Comparative Example 3]
In Example 1, an inner layer circuit board (“MCL-E705G” manufactured by Hitachi Chemical Co., Ltd., a conductor layer thickness of 35 μm, a total thickness of 0.4 mm) is used as an inner layer circuit board (“MCL-E679FGR” manufactured by Mitsubishi Gas Chemical Company, Inc.) The thickness of the layer was changed to 35 μm (total thickness: 0.4 mm). Except for the above, a multilayer printed wiring board was obtained in the same manner as in Example 1.

  Evaluation about the insulating resin film and circuit board obtained by the above Example and the comparative example was performed as follows. The results are shown in the table below.

[Measurement of coefficient of thermal expansion (CTE) of inner layer substrate]
Based on the provisions of JIS C 6481-1996 (5.19), the circuit on the inner layer circuit board was removed by etching, and the thermal expansion coefficient of the inner layer circuit board was measured by the TMA method.

[Measurement of glass transition temperature of insulating layer]
Resin varnish is evenly applied with a die coater on the release treatment surface of a PET film (38 μm) treated with an alkyd release agent so that the thickness of the resin composition layer after drying is 25 μm. And it dried at 80-120 degreeC (average 100 degreeC) for 5 minutes, and the insulating resin film was obtained. Next, the insulating resin film was thermally cured under the conditions described in Examples and Comparative Examples, and a small piece of the insulating resin film obtained by thermosetting the resin composition layer was used as a sample. The sample was measured in a “tensile mode” using a model DMS-6100 manufactured by Seiko Instruments Inc. as a thermomechanical analyzer (DMA). This measurement was performed in the range of 25 ° C. to 240 ° C. at a temperature increase of 2 ° C./min. A value obtained by rounding off the first decimal place of the maximum value of the loss tangent (tan δ) obtained by the ratio between the storage elastic modulus (E ′) and the loss elastic modulus (E ″) obtained by the measurement was taken as the glass transition temperature.

[Evaluation of warpage behavior]
The multilayer printed wiring boards in the examples and comparative examples were cut into five 45 mm square pieces and then passed once through a reflow apparatus (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) having a peak temperature of 260 ° C. The conditions are based on IPC / JEDEC J-STD-020C). Next, using a shadow moire device (Thermoire AXP manufactured by Akrometrix), the multilayer printed wiring board is heated from the lower part of the multilayer printed wiring board with a temperature profile conforming to IPC / JEDEC J-STD-020C (peak temperature 260 ° C.). The warpage behavior of a 10 mm square portion at the center of the plate was measured. Performed for 5 pieces, the difference between the maximum height and the minimum height of the obtained displacement data is “x” when one sample is 40 μm or more in the whole temperature range, and “x” when all samples are less than 40 μm. ○ ”.

[Evaluation of delamination]
For multilayer printed wiring boards after warpage behavior evaluation, the area where delamination occurs between the circuit on the inner circuit board and the insulating layer, or between the insulating layer and the conductor layer using “FineSAT FS300III” manufactured by Hitachi Power Solutions. confirmed. “×” means that the delamination area is 10% or more with respect to the area of 20.25 cm ² of the multilayer printed wiring board, “△” means that the area is 10% or more, and “△” means that it is less than 1%. Was marked as “◯”.

Claims (7)

(A) A step of preparing an insulating resin film including a support and a resin composition layer formed on the support and formed from a resin composition including a cyanate ester resin;
(B) A step of laminating an insulating resin film on an inner layer substrate having a coefficient of thermal expansion of 10 ppm or less so that the resin composition layer is bonded to the inner layer substrate;
(C) a step of thermosetting the resin composition layer to form an insulating layer having a glass transition temperature of T1 (° C.);
(E) The manufacturing method of a printed wiring board including the process of heating an insulating layer by T2 (degreeC) so that the following general formula (1) may be satisfy | filled.
5 ° C ≦ T1-T2 ≦ 50 ° C (1)   The manufacturing method of the printed wiring board of Claim 1 including the process of cooling (D) an insulating layer to room temperature before a (E) process.   (E) The manufacturing method of the printed wiring board of Claim 1 or 2 which heats an insulating layer for 5 to 90 minutes at T2 (degreeC) in a process.   (C) The manufacturing method of the printed wiring board of any one of Claims 1-3 in which glass transition temperature T1 (degreeC) of an insulating layer satisfy | fills 100 degreeC <= T1 <= 200 degreeC in a process.   The manufacturing method of the printed wiring board of any one of Claims 1-4 including the process of roughening a (G) insulating layer after the (E) process.   The manufacturing method of the printed wiring board of Claim 5 including the process of forming a conductor layer in the (H) insulating layer surface after (G) process.   The manufacturing method of the printed wiring board of any one of Claims 1-6 whose thickness of an insulating layer is 100 micrometers or less.