JP2006229038A - Manufacturing method of multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a multilayer printed wiring board with little signal loss and excellent adhesion of a conductor layer.
An uncured or semi-cured resin layer made of a curable composition containing an insulating polymer and a curing agent is formed on an inner layer substrate whose outermost layer is a conductor layer, and the surface thereof is formed. After contacting a compound having a structure capable of coordinating with a metal, the resin layer is cured to form an electrical insulation layer, and then the surface of the electrical insulation layer is hydrophilized, and then the electrical insulation layer surface is dried. And a compound having a structure capable of coordinating with a metal is contacted, and then a conductor layer is formed by a plating method.
[Selection figure] None

Description

  The present invention relates to a method for producing a multilayer printed wiring board, and more particularly to a method for producing a multilayer printed wiring board having excellent pattern adhesion.

As electronic devices become smaller and more multifunctional, circuit boards used in electronic devices are required to have higher density.
In order to increase the density of a circuit board, the circuit board is generally multilayered. A multilayer circuit board is usually obtained by laminating an electric insulation layer on the surface of an inner layer board having a conductor layer formed on the outermost layer, and forming a conductor layer on the electric insulation layer. The electrical insulating layer and the conductor layer can be alternately laminated in several layers as necessary.

  In a multilayer circuit board, in order to obtain electrical insulation characteristics, the interface between the conductor layer provided as the outermost layer of the inner layer board and the electrical insulation layer, and the interface between this electrical insulation layer and the conductor layer formed thereon, etc. The adhesion between the layers is particularly required. For improving the adhesion, for example, Patent Document 1 proposes a method of roughening the surface of the electrical insulating layer. Patent Document 2 proposes that an electroless plating adhesive containing a polymer component such as rubber or resin is applied on the electric insulating layer after roughening. In Patent Document 3, a conductive layer on an inner substrate is chemically roughened with a corrosive solution, and then the surface is contact-treated with a specific triazine thiol compound to form a layer of a curable insulating resin containing an epoxy resin or the like. Furthermore, a technique for forming a conductor layer on the electrical insulating layer is disclosed.

On the other hand, it is known that when the electrical insulating layer is roughened, noise easily enters the signal and signal loss due to surface roughness occurs. As the frequency of signals increases, the effect of the skin effect increases, and this problem has come to be emphasized. However, when a conductor layer is formed by plating on a smooth electrical insulating layer surface in order to suppress signal loss, there arises a problem that adhesion is lowered.
In order to solve these two conflicting problems, in Patent Document 4, a carboxyl group-containing polymer as an insulating polymer and a curing agent as an insulating polymer on an inner layer substrate whose outermost layer is a conductor circuit layer (conductor layer). After forming an uncured or semi-cured resin layer using a curable composition containing a polyvalent epoxy compound, the surface of the resin layer is contacted with a compound having a structure capable of coordinating with a metal, A method of manufacturing a multilayer circuit board is disclosed in which the resin layer is cured to form an electrical insulation layer, a conductor layer is formed on the surface of the electrical insulation layer, and then a conductor circuit layer (conductor layer) is formed. Yes. With this technique, even when a conductor layer is formed on a smooth electrical insulating layer, high adhesion between the electrical insulating layer and the conductor layer and low signal loss can be achieved simultaneously.

  By the way, the electroless plating processing apparatus for manufacturing a conventional multilayer circuit board includes swelling processing, hydrophilization processing, neutralization reduction processing, cleaner conditioner processing, soft etch processing, pickling processing, catalyst application processing, catalyst activation processing, The electroless plating treatment and the water washing treatment are each performed in dedicated treatment tanks. Therefore, when a substrate is transported to each processing tank, a drying process for removing water or the like adhering to the surface may be performed. For example, the substrate is subjected to a hydrophilic treatment, or a hydrophilic treatment and a neutralization reduction treatment, and then dried by a heat treatment or the like, and conveyed to the next step, and a conductor layer is formed by a plating method.

JP-A-11-286562 Japanese Patent Laid-Open No. 2001-192844 JP-A-11-54936 JP 2003-158373 A

  Therefore, the present inventors performed a hydrophilization treatment or a hydrophilization treatment and a neutralization reduction treatment on the substrate on which the electrical insulation layer is formed according to the method of Patent Document 4, and then the surface of the electrical insulation layer by plating. An attempt was made to form a conductor layer. However, as a result, it has been found that sufficient adhesion between the electrical insulating layer and the conductor layer may not be obtained. As a result of further studies, it was confirmed that the adhesion between the electrical insulating layer and the conductor layer might be lowered depending on the degree of drying of the surface of the electrical insulating layer after the neutralization reduction treatment.

  The present invention has been made in view of the above problems, and its purpose is to perform a hydrophilization treatment, or a hydrophilization treatment and a neutralization reduction treatment, and then perform a metal coordination ability on a dried electrical insulating layer. Of a multilayer circuit board that can improve the adhesion between the electrical insulating layer and the conductor layer and satisfy the required quality for signal loss. It is to provide a manufacturing method.

  In order to achieve the above-mentioned object, the present inventors performed a hydrophilization treatment, or a plating method on the surface of the electrically insulating layer which has been dried after the hydrophilization treatment and the neutralization reduction treatment, and has not been roughened. In order to obtain a multilayer circuit board that achieves both high adhesion at the interface between the electrical insulating layer and the conductor layer and low signal loss even when the conductor layer is formed by the above-mentioned method, intensive studies have been made. As a result, a compound having a structure capable of metal coordination is brought into contact with the surface of the electrical insulating layer which has been dried after the hydrophilization treatment or the hydrophilization treatment and the neutralization reduction treatment, and plating is grown thereon. It has been found that by forming the conductor layer circuit layer, the thermosetting resin composition having excellent adhesion and flatness can be stably obtained regardless of the degree of drying of the surface of the electrically insulating layer after the hydrophilic treatment. Based on this finding, the present invention has been completed.

Thus, according to the present invention, the following inventions 1 to 5 are provided.
1. On the inner layer substrate whose outermost layer is a conductor layer, an uncured or semi-cured resin layer using a curable composition containing an insulating polymer and a curing agent is formed, and this surface is provided with a metal. After contacting a compound having a recognizable structure, the resin layer is cured to form an electrical insulation layer, and then the surface of the electrical insulation layer is hydrophilized, and then the surface of the electrical insulation layer is dried, and further the metal A method for producing a multilayer printed wiring board, comprising contacting a compound having a coordinable structure with a conductive layer after plating.
2. 2. The multilayer printed wiring according to 1 above, wherein the hydrophilization treatment is a method in which a solution of an oxidizing compound selected from the group consisting of permanganate, chromate and dichromate is brought into contact with the surface of the electrical insulating layer. A manufacturing method of a board.
3. The manufacturing method of the multilayer printed wiring board in any one of said 1-2 whose electrical insulation layer contains resin and / or a filler soluble in the solution of the said oxidizing compound.
4). The manufacturing method of the multilayer printed wiring board in any one of said 1-3 including the process of heat-processing the metal thin film layer formed in the electrical insulating layer.
5. The multilayer printed wiring board manufactured by the method in any one of Claims 1-4.

  According to the present inventor, even if a conductor layer is formed by plating on the surface of the electrically insulating layer that is dried after the hydrophilization treatment and is not substantially roughened, the interface between the electrically insulating layer and the conductor layer has high adhesion. A multilayer circuit board that realizes both compatibility and low signal loss can be obtained.

The manufacturing method of the multilayer printed wiring board of this invention can be divided into the following five processes.
(Process A) Uncured using a curable composition containing an insulating polymer and a curing agent on an inner layer substrate whose outermost layer is a conductor layer (hereinafter sometimes referred to as a first conductor layer). Alternatively, a semi-cured resin layer is formed, and a compound having a structure capable of coordinating with a metal is brought into contact with this surface.
(Step B) The resin layer is cured to form an electric insulation layer, and the surface of the obtained electric insulation layer is subjected to a hydrophilic treatment. Here, following the hydrophilization treatment, the neutralization reduction treatment can be performed on the surface of the electrical insulating layer before performing the step C.
(Step C) The electrical insulating layer is dried.
(Step D) A compound having a structure capable of coordinating with a metal is brought into contact with the surface of the electrical insulating layer.
(Step E) A conductor layer (hereinafter sometimes referred to as a second conductor layer) is formed on the electrical insulating layer by a plating method.
Each step will be described in detail below.

(Process A)
The inner layer substrate related to this step is a substrate having one or more electrical insulating layers and conductor layers, and the outermost layer being a conductor layer.
The conductor layer constituting the inner layer substrate is usually made of a conductive metal.
The electrical insulating layer constituting the inner layer substrate may be an inorganic compound such as silicon oxide or alumina, or an alicyclic olefin polymer, an epoxy resin, a maleimide resin, a (meth) acrylic resin, a diallyl phthalate resin, a triazine resin, or an aromatic poly It consists of organic compounds, such as ether polymers, cyanate ester polymers, and insulating polymers such as polyimide. In addition, the inner layer substrate may contain glass fibers, resin fibers, etc. in order to improve strength.
The thickness of the inner layer substrate excluding the thickness of the outermost conductor layer is usually 10 μm to 2 mm, preferably 30 μm to 1.6 mm, more preferably 40 μm to 1 mm.
Specific examples of such an inner layer substrate include a printed wiring board and an insulating substrate. In this case, a conductor layer is formed on the surface of the electrical insulating layer.

On this inner layer substrate, an uncured or semi-cured resin layer is formed using a curable composition containing an insulating polymer and a curing agent.
Here, the uncured resin layer is in a state where substantially the entire resin layer can be dissolved in a solvent in which the insulating polymer constituting the resin layer can be dissolved. The semi-cured resin layer is in a state of being cured to such an extent that it can be further cured by heating, and is preferably partially (specifically, in a solvent in which the insulating polymer constituting the resin layer can be dissolved. 7% by weight or more) or a swelling ratio of the volume when the resin layer is immersed in the solvent for 24 hours is 200% or more before immersion.

  The insulating polymer constituting the curable composition used for forming the uncured or semi-cured resin layer is not limited as long as it has electrical insulation. For example, epoxy resin, maleimide resin, (meth) acrylic resin, diallyl phthalate resin, triazine resin, alicyclic olefin polymer, aromatic polyether polymer, benzocyclobutene polymer, cyanate ester polymer, liquid crystal polymer, polyimide, etc. Is mentioned. Among these, alicyclic olefin polymers, aromatic polyether polymers, benzocyclobutene polymers, cyanate ester polymers or polyimides are preferred, alicyclic olefin polymers or aromatic polyether polymers are particularly preferred, Alicyclic olefin polymers are particularly preferred.

Although there is no special restriction | limiting in the weight average molecular weight of an insulating polymer, Usually, 10,000-1,000,000, Preferably it is 50,000-500,000. Insulating polymer component 100 in which a polymer having a weight average molecular weight Mw of 10,000 to 1,000,000 is contained in the curable composition is easy to control the degree of roughness of the electrical insulating layer by the oxidation treatment. It is desirable that 20 parts by weight or more, preferably 30 parts by weight or more is present in the parts by weight.
In the present invention, the weight average molecular weight Mw is a weight average molecular weight in terms of polystyrene or polyisoprene measured by gel permeation chromatography (GPC).

  An alicyclic olefin polymer which is a particularly preferable insulating polymer is a polymer of an unsaturated hydrocarbon having an alicyclic structure. Specific examples of alicyclic olefin polymers include ring-opening polymers of norbornene monomers and hydrogenated products thereof, addition polymers of norbornene monomers, addition weights of norbornene monomers and vinyl compounds. Examples thereof include a polymer, a monocyclic cycloalkene polymer, an alicyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer and a hydrogenated product thereof, and an aromatic ring hydrogenated product of an aromatic olefin polymer. Among these, ring-opening polymers of norbornene monomers and hydrogenated products thereof, addition polymers of norbornene monomers, addition polymers of norbornene monomers and vinyl compounds, aromatic olefin polymers An aromatic ring hydrogenated product is preferable, and a hydrogenated product of a ring-opening polymer of a norbornene monomer is particularly preferable.

  The alicyclic olefin polymer preferably has a polar group. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. An anhydride (carbonyloxycarbonyl) group is preferred.

The alicyclic olefin polymer is usually 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . Addition polymerization or ring-opening polymerization of an alicyclic olefin having a norbornene ring such as 1 ^7,10 ] dodec-3-ene or tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, If necessary, it can be obtained by hydrogenating the unsaturated bond portion, or by addition polymerization of an aromatic olefin and hydrogenating the aromatic ring portion of the polymer. The alicyclic olefin polymer having a polar group is, for example, 1) by introducing a polar group into the alicyclic olefin polymer by a modification reaction, and 2) copolymerizing a monomer containing the polar group. It can be obtained by copolymerization as a component, or 3) by copolymerizing a monomer containing a polar group such as an ester group as a copolymerization component and then hydrolyzing the ester group.
Moreover, an alicyclic olefin polymer can also be obtained by copolymerizing an alicyclic olefin and / or an aromatic olefin, and these monomers (for example, 1-hexene etc.) which can be copolymerized.

  The glass transition temperature of the alicyclic olefin polymer can be appropriately selected according to the purpose of use, but is usually 50 ° C. or higher, preferably 70 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 125 ° C. or higher.

  Any curing agent may be used as long as it forms a crosslinked structure by heating and cures. As the curing agent, a known thermosetting agent such as an ionic curing agent, a radical curing agent, or a curing agent having both ionic and radical properties can be used, and in particular, bisphenol A bis (propylene glycol glycidyl ether) ether. Polyhydric epoxy compounds such as glycidyl ether type epoxy compounds, alicyclic epoxy compounds, and glycidyl ester type epoxy compounds are preferred. The mixing ratio of the curing agent is usually in the range of 1 to 100 parts by weight, preferably 5 to 80 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the insulating polymer.

  Moreover, it becomes easy to obtain an electrical insulating film having high heat resistance by using a curing accelerator in addition to the curing agent. For example, when a polyvalent epoxy compound is used as the curing agent, a curing accelerator such as a tertiary amine compound such as a triazole compound or an imidazole compound or a boron trifluoride complex compound may be used.

In the curable resin composition, in the case of adopting a method of bringing the oxidation treatment liquid into contact with the surface of the electric insulation layer in the hydrophilic treatment of the electric insulation layer in the step B, a resin component or filler that can be dissolved in the oxidation treatment liquid It is good to include. The resin component that can be dissolved in the oxidation treatment liquid will be described in detail in the description of the step B.
Moreover, other components can be mix | blended with the curable composition concerning this invention as needed. For example, other components include flame retardants, soft polymers, heat stabilizers, weathering stabilizers, anti-aging agents, leveling agents, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments Natural oils, synthetic oils, waxes, emulsions, fillers, magnetic materials, dielectric property modifiers, tougheners and the like. The blending ratio is appropriately selected within a range that does not impair the object of the present invention.

Usually, when each component which comprises the curable composition mentioned above is mix | blended with a liquid medium and it is set as the varnish of a curable composition, formation of a resin layer becomes easy. Examples of the solvent used for preparing the varnish include aromatic hydrocarbon organic solvents such as toluene, xylene, ethylbenzene and trimethylbenzene; aliphatic hydrocarbon organic solvents such as n-pentane, n-hexane and n-heptane; Aliphatic hydrocarbon organic solvents such as pentane and cyclohexane; Halogenated hydrocarbon organic solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene; Ketone organic solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Can be mentioned.
There is no special restriction | limiting in the method of obtaining a varnish, For example, it can obtain by mixing each component which comprises a curable composition, and an organic solvent. The mixing method of each component may be in accordance with ordinary methods, for example, stirring using a stirrer and a magnetic stirrer, high speed homogenizer, dispersion, planetary stirrer, twin screw stirrer, ball mill, three rolls, etc. And so on. The temperature at the time of mixing is in a range where the reaction by the curing agent does not affect the workability, and is preferably below the boiling point of the organic solvent used at the time of mixing from the viewpoint of safety.
The amount of the organic solvent used is appropriately selected according to the purpose of controlling the thickness or improving the flatness, but the solid content concentration of the varnish is usually 5 to 70% by weight, preferably 10 to 65% by weight, more preferably. Is in the range of 20 to 60% by weight.

There is no particular limitation on the method of forming the resin layer on the inner layer substrate, but a film-like or sheet-like molded product of a curable composition containing an insulating polymer and a curing agent is pasted so as to contact the inner layer substrate. A method (A1) for forming a resin layer together, or applying a varnish of a curable composition containing an insulating polymer and a curing agent on an inner layer substrate and drying to apply an uncured or semi-cured resin layer The method (A2) which forms is mentioned.
It is preferable to form the resin layer by the method (A1) from the viewpoint of high in-plane uniformity of adhesion with the metal thin film layer formed on the electrical insulating layer obtained by curing the resin layer.

  In the case of forming an uncured or semi-cured resin layer by the method (A1), in order to improve the adhesion between the conductor layer on the inner substrate surface and the electrical insulating layer, a film-shaped or sheet-shaped molded body of the curable composition It is preferable to pretreat the surface of the inner layer substrate on which the conductor layer is formed before bonding the layers. The pretreatment method is not particularly limited, and a known technique can be used. For example, if the conductor layer on the inner layer substrate is made of copper, a strong alkaline oxidizing solution is brought into contact with the inner layer substrate surface to form a tufted copper oxide layer on the first conductor layer surface. Oxidation method, method of oxidizing the surface of the first conductor layer by the previous method and then reducing with sodium borohydride, formalin, etc., method of depositing and roughening the plating on the first conductor layer, organic acid And a method of eluting and roughening the copper grain boundary of the first conductor layer, a method of forming a primer layer with a thiol compound or a silane compound, and the like. Among these, from the viewpoint of easily maintaining the shape of the fine wiring pattern, the primer layer is formed by a method of eluting and roughening the copper grain boundary of the first conductor layer by contacting with an organic acid, a thiol compound or a silane compound, etc. The method of forming is preferred.

  The thickness of the film-like or sheet-like molded product of the curable composition used in the method (A1) is usually 0.1 to 150 μm, preferably 0.5 to 100 μm, more preferably 1.0 to 80 μm.

This film-like or sheet-like molded product is usually obtained by molding a curable composition by a solution casting method, a melt casting method, or the like. In the case of molding by the solution casting method, the organic solvent is dried and removed after applying the varnish to the support.
Resin film (carrier film) as a support used in the solution casting method
And metal foil. As the resin film, a thermoplastic resin film is usually used. Specific examples include a polyethylene terephthalate film, a polypropylene film, a polyethylene film, a polycarbonate film, a polyethylene naphthalate film, a polyarylate film, and a nylon film. Among these resin films, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable from the viewpoints of heat resistance, chemical resistance, peelability after lamination, and the like. Examples of the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil. From the viewpoint of good conductivity and low cost, a copper foil, particularly an electrolytic copper foil or a rolled copper foil is preferred. The thickness of the support is not particularly limited, but is usually 1 μm to 150 μm, preferably 2 μm to 100 μm, more preferably 3 μm to 50 μm from the viewpoint of workability and the like. The surface average roughness of the support is such that Ra is 300 nm or less, preferably 150 nm or less, more preferably 100 nm or less. When the surface average roughness Ra of the support is too large, the surface average roughness Ra of the electrical insulating layer is increased and it is difficult to form a fine conductor pattern.

  Examples of the method for applying the varnish of the curable composition to the support include dip coating, roll coating, curtain coating, die coating, and slit coating. The conditions for removing and drying the organic solvent are appropriately selected depending on the type of the organic solvent, the drying temperature is usually 20 to 300 ° C., preferably 30 to 200 ° C., and the drying time is usually 30 seconds to 1 hour, preferably Is 1 to 30 minutes.

  In the method (A1), there is no particular limitation on the method of laminating the film-shaped or sheet-shaped molded product of the curable composition on the inner layer substrate. For example, a film-shaped or sheet-shaped molded product with a support is Lamination is performed so that the molded product is in contact with the conductor layer, and pressure bonding (lamination) is performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator, etc. A method of bonding the two so that there is no substantial void at the interface is mentioned. The thermocompression bonding is preferably performed under vacuum in order to improve the embedding property in the wiring and suppress the generation of bubbles and the like. The temperature during thermocompression bonding is usually 30 to 250 ° C., preferably 70 to 200 ° C., the crimping force is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa, and the crimping time is usually 30 seconds to 5 hours, preferably 1 minute. -3 hours, and the pressure is usually reduced to 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa.

  The number of the molded products laminated on the inner layer substrate may be two or more. For example, for the purpose of improving the flatness of the electrical insulating layer or increasing the thickness of the electrical insulating layer, the inner layer on which the molded product is bonded. Another film-shaped or sheet-shaped molded product may be bonded to the substrate so as to be in contact with the molded product. When an uncured or semi-cured resin layer is formed by laminating a plurality of film-like or sheet-like molded products to the inner layer substrate, the last contact with the compound having a structure capable of coordinating to the metal is performed. It becomes a molded product.

  When an uncured or semi-cured resin layer is formed by the method (A2), the varnish of the curable composition described above may be directly applied onto the inner layer substrate and dried. The method and conditions for application and drying may be the same as those for forming a film-like or sheet-like molded product of the curable composition.

  In (Step A), a compound having a structure capable of coordinating with a metal is brought into contact with the surface of an uncured or semi-cured resin layer formed on the inner layer substrate. When forming a resin layer by laminating a film-like or sheet-like molded product of the curable composition on the inner layer substrate, when a molded product with a support is used as the molded product, the support is peeled off. This step is performed.

  A compound having a metal coordination ability (hereinafter, sometimes referred to as a coordination structure-containing compound) has a functional group capable of giving care to a metal. Preferred specific examples include an amino group, a thiol group, Examples thereof include compounds having a lone pair such as a compound having a functional group capable of coordinating to a metal such as a carboxyl group or a cyano group, or a heterocyclic compound having a coordination ability with a metal. Among these, a heterocyclic compound containing a nitrogen atom, oxygen atom or sulfur atom in the ring is particularly preferred, and a heterocyclic compound containing a nitrogen atom is particularly preferred. Of course, such a heterocyclic compound may further have another functional group capable of coordinating to a metal. Furthermore, a heterocyclic compound having a functional group capable of coordinating to a metal is preferable in terms of providing higher pattern adhesion.

  Among the coordination structure-containing compounds, it reacts with components in the curable resin composition, and these compounds are firmly held on the surface of the resin substrate formed in the next step, so that imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-mercaptomethylbenzimidazole, 2-ethylimidazole-4-dithiocarboxylic acid, 2-methylimidazole-4-carboxylic acid, 1- (2-aminoethyl) -2-methylimidazole Imidazoles such as 1- (2-cyanoethyl) -2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, benzimidazole, 2-ethyl-4-thiocarbamoylimidazole; pyrazole, 3-amino-4 -Pyrazoles such as cyano-pyrazole; 1,2,4-triazole, 2- Triazoles such as mino-1,2,4-triazole, 1,2-diamino-1,2,4-triazole, 1-mercapto-1,2,4-triazole; 2-aminotriazine, 2,4-diamino Preferred examples include triazines such as -6- (6- (2- (2-methyl-1-imidazolyl) ethyl) triazine 2,4,6-trimercapto-s-triazine-trisodium salt;

  When these coordination structure-containing compounds are used, when the resin layer is cured, the crosslinking density on the surface of the resin layer can be increased and the hydrophilicity can be increased. For this reason, the strength of the electrical insulation layer is maintained by the hydrophilic treatment on the surface of the electrical insulation layer described in detail below, while the resin and filler soluble in the hydrophilic treatment solution contained in the electrical insulation layer are removed. Can be easily.

A method for bringing such a coordination structure-containing compound into contact with the uncured or semi-cured resin layer surface is not particularly limited. Specific examples include a dipping method in which a coordination structure-containing compound is dissolved in water or an organic solvent to form a solution, and the inner layer substrate on which the resin layer is formed is immersed in this solution, or this solution is applied to the resin layer surface. The spray method etc. which apply | coat with spray etc. are mentioned. The contact operation may be repeated once or twice or more.
The temperature at the time of contact can be arbitrarily selected in consideration of the boiling point, melting point, operability and productivity of the coordination structure-containing compound and its solution, but is usually 10 to 100 ° C., preferably 15 to 65 ° C. To do. The contact time can be arbitrarily selected according to the amount of the coordination structure-containing compound to be adhered to the surface of the molded product, the concentration of the solution, the productivity of the printed wiring board, etc., but usually 0.1 to 360 minutes. , Preferably 0.1 to 60 minutes.
Thereafter, an inert gas such as nitrogen is sprayed for the purpose of removing excess coordination structure-containing compound and drying the substrate; usually 30 to 180 ° C., preferably 50 to 150 ° C. for 1 minute or more, preferably 5 to 5 ° C. It can be treated in an oven for 120 minutes; washed with a solvent; washed with a solvent and then heated to dry.

When the coordination structure-containing compound is dissolved in a solvent and used, the solvent to be used is not particularly limited, and the resin layer after lamination does not easily dissolve, and it is only necessary to select one that dissolves the coordination structure-containing compound. Water, ethers such as tetrahydrofuran, alcohols such as ethanol and isopropanol, ketones such as acetone, polar solvents such as cellosolves such as ethyl cellosolve acetate, and mixtures thereof. There is no particular limitation on the concentration of the coordination structure-containing compound in the coordination structure-containing compound solution, but the coordination structure-containing compound is usually 0.001 to 70% by weight from the viewpoint of operability in this step, preferably 0.01 to 50% by weight.
Of course, when the coordination structure-containing compound is a liquid at the operating temperature and there is no problem in the operation of bringing the coordination structure-containing compound into contact with the surface of the uncured or semi-cured resin layer, the compound is not dissolved in a solvent and used as it is. It is also possible.
In the present invention, the solution of the coordination structure-containing compound is mainly composed of the above-mentioned coordination structure-containing compound, and as a component other than the coordination structure-containing compound, an uncured or semi-cured resin layer and a coordination structure Examples thereof include surfactants and other additives used for the purpose of improving the wetting with the containing compound solution. The amount of these additives to be used is 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the coordination structure-containing compound from the viewpoint of ensuring adhesion.

(Process B)
Subsequent to the above step A, the uncured or semi-cured resin layer after being brought into contact with the compound having metal coordination ability on the surface is cured to form an electrical insulating layer.
The resin layer is usually cured by heating the resin layer (the entire inner layer substrate on which the resin layer is formed). Curing conditions are appropriately selected according to the type of the curing agent, but the temperature for curing is usually 30 to 400 ° C., preferably 70 to 300 ° C., more preferably 100 to 200 ° C., and the curing time is Usually 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an oven.

Normally, when forming a multilayer printed wiring board, an opening for forming a via hole is formed in the electrical insulating layer before forming the metal thin film layer in order to connect the first conductor layer and the second conductor layer formed later. Form. The opening for forming the via hole can be formed by chemical processing such as photolithography, or physical processing such as drilling, laser, or plasma etching. From the viewpoint that a finer via hole can be formed without degrading the characteristics of the electrical insulating layer, a method using a laser such as a carbon dioxide laser, an excimer laser, or a UV-YAG laser is preferable.
Therefore, the electrical insulating layer according to the next step C usually has an opening for forming a via hole.

Next, a hydrophilic treatment is performed using a hydrophilic treatment solution having a predetermined concentration. As the hydrophilization treatment liquid, an oxidizing solution selected from the group consisting of permanganate, chromate and dichromate is preferably used, and permanganate is particularly preferably used. Moreover, it is preferable to mix an alkali hydroxide with the hydrophilic treatment liquid.
The permanganate is an alkali metal permanganate, and potassium permanganate and sodium permanganate are preferably used. Alkali hydroxide is an alkali metal hydroxide, and potassium hydroxide and sodium hydroxide are preferably used.

  A particularly preferred hydrophilization treatment liquid containing permanganate and alkali hydroxide is obtained by dissolving permanganate and alkali hydroxide in water, and the concentration of permanganate is usually 50 g / liter or more. 150 g / liter or less, preferably 60 g / liter or more and 100 g / liter or less, and the concentration of the alkali hydroxide is usually 0.6 or more and 1.5 or less, preferably 0.95 or more and 1.2 or less. It adjusted so that it might become the following. If the concentration is within this range, good adhesion can be obtained.

  The method for bringing the hydrophilization treatment solution composed of a mixed solution of permanganate and alkali hydroxide into contact with the electrical insulating layer is not particularly limited. For example, a dipping method in which the electrical insulating layer is immersed in an oxidizing compound solution, the surface Any method may be used, such as a liquid filling method in which an oxidizing compound solution is placed on an electrical insulating layer using tension, or a spray method in which an oxidizing compound solution is sprayed onto a substrate. The contact operation may be performed once or twice or more.

When oxidizing the surface of the electrical insulating layer with a hydrophilic treatment liquid, if a hydrophilic polymer or an inorganic filler is contained in the thermosetting slurry before forming the electrical insulation layer, Since the electrically insulating polymer in the thermosetting slurry and a fine sea-island structure are formed and then selectively dissolved, the surface average roughness can be adjusted to a desired value.
In the present invention, the surface average roughness Ra of the electrical insulating layer is 0.05 μm or more and less than 0.2 μm, preferably 0.06 μm or more and 0.1 μm or less, and the surface ten-point average roughness Rzjis is 0.3 μm or more. It is less than 4 μm, preferably 0.5 μm or more and 3 μm or less.
Here, Ra is the center line average roughness shown in JIS B 0601-2001, and the surface 10-point average roughness Rzjis is the 10-point average roughness shown in JIS B 0601-2001 Annex 1.

Examples of polymers soluble in the hydrophilization treatment liquid include liquid epoxy resins, polyester resins, bismaleimide-triazine resins, silicone resins, polymethylmethacrylic resins, natural rubber, styrene rubber, isoprene rubber, butadiene rubber. Nitrile rubber, ethylene rubber, propylene rubber, urethane rubber, butyl rubber, silicone rubber, fluorine rubber, norbornene rubber, ether rubber and the like.
There is no particular limitation on the blending ratio of the polymer soluble in the hydrophilic treatment liquid, and it is usually 1 to 30 parts by weight, preferably 3 to 25 parts by weight, more preferably 5 to 100 parts by weight of the insulating polymer. ~ 20 parts by weight.

  Examples of inorganic fillers soluble in the hydrophilization treatment solution include calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina, Examples thereof include magnesium hydroxide, aluminum hydroxide, barium sulfate, silica, talc, and clay. Among these, calcium carbonate and silica are suitable for obtaining a fine rough surface shape because fine particles are easily obtained and are easily eluted with a filler-soluble aqueous solution. These inorganic fillers may be treated with a silane coupling agent or an organic acid such as stearic acid.

Moreover, it is preferable that the inorganic filler to be added is non-conductive that does not deteriorate the dielectric properties of the electrical insulating layer. The shape of the inorganic filler is not particularly limited and may be spherical, fibrous, plate-like, or the like, but is preferably a fine powder to obtain a fine rough surface shape. The average particle size of the inorganic filler is 0.008 μm or more and less than 2 μm, preferably 0.01 μm or more and less than 1.5 μm, particularly preferably 0.02 μm or more and less than 1 μm. If the average particle size is too small, uniform adhesion may not be obtained in the case of a large substrate. Conversely, if the average particle size is too large, a large rough surface is generated in the electrical insulating layer, and a high-density wiring pattern is obtained. There is no possibility.
The blending amount of the inorganic filler soluble in the hydrophilic treatment liquid is appropriately selected according to the required degree of adhesion, but is usually 1 to 80 parts by weight with respect to 100 parts by weight of the polymer. Preferably it is 3-60 weight part, More preferably, it is 5-40 weight part.
Polymers and inorganic fillers that are soluble in the hydrophilic treatment liquid as described above can be used as a part of a flame retardant aid, a heat-resistant stabilizer, a dielectric property adjusting agent, a toughening agent, and the like.

  After the hydrophilic treatment of the electrical insulating layer, the surface of the electrical insulating layer is usually washed with water in order to remove the oxidizing compound. If a substance that cannot be washed with water alone is attached, wash the substance with a dissolvable cleaning solution or contact with other compounds to make it soluble in water, and then wash with water. You can also. For example, when an alkaline aqueous solution such as a potassium permanganate aqueous solution or a sodium permanganate aqueous solution is brought into contact with the electrical insulating layer, hydroxyamine sulfate or hydroxyamine sulfate and sulfuric acid are used for the purpose of removing the generated manganese dioxide film. And neutralization reduction treatment with an acidic aqueous solution such as a mixed solution. The neutralization reduction step can be performed after the drying step described later.

(Process C)
Next, a drying process is performed to remove water adhering to the surface of the electrical insulating layer. Specific drying conditions are not particularly limited, and may be appropriately selected in consideration of the composition of the electrical insulating layer. For example, air or an inert gas such as nitrogen is sprayed; Dry at high temperature gas (air, nitrogen gas, argon gas, etc.) at a temperature of 50 ° C., preferably 50-160 ° C. for 1 minute or longer, preferably 5-120 minutes, with a hot air dryer or blower dryer that blows the substrate on the substrate; Can be processed. Further, a far-infrared dryer that evaporates residual moisture and the like can be used by urging the temperature rise inside and outside the substrate by irradiation with far-infrared rays.

(Process D)
Through affirmative C, the coordination structure-containing compound is brought into contact with the electrical insulating layer having at least a dry surface. The coordination structure-containing compound is not particularly limited, and may be selected from, for example, the compound group exemplified in Step A. Even if the same compound as that used in Step A is selected, a different compound is selected. Also good.
Further, the method for bringing the coordination structure-containing compound into contact is not particularly limited, and can be selected from, for example, the same method exemplified in Step A. Even if the same method as that adopted in Step A is selected, Different methods may be selected.

(Process E)
Subsequently, after the surface of the dried electrical insulating layer is brought into contact with the coordination structure-containing compound, a metal thin film layer is formed. A second conductor layer is formed by plating on the surface of the electrical insulating layer and the inner wall surface of the via hole forming opening.
As a method of forming the second conductor layer by the plating method, first, a metal thin film is formed on the inner layer substrate or the electrical insulating layer by an electroless plating method, and then a resist pattern for plating is formed on the metal thin film, There is a method in which after a metal layer is grown on a pattern by electrolytic plating using a metal thin film, the resist is removed, and then the metal is etched to remove the metal thin film and form a conductor layer.

When forming a metal thin film layer by electroless plating, it is advisable to adsorb catalyst nuclei such as silver, palladium, zinc and cobalt on the metal thin film layer before forming the metal thin film layer on the surface of the electrical insulating layer. It is common.
The method for attaching the catalyst nucleus to the electrical insulating layer is not particularly limited, and a metal compound such as silver, palladium, zinc, cobalt, or a salt or complex thereof is added to water or an organic solvent such as alcohol or chloroform in an amount of 0.001 to 10%. For example, a method of reducing a metal after dipping in a solution (which may contain an acid, an alkali, a complexing agent, a reducing agent, etc., if necessary) dissolved in a concentration by weight is included.

As the electroless plating solution used in the electroless plating method, a known autocatalytic electroless plating solution may be used. The metal species, reducing agent species, complexing agent species, hydrogen ion concentration, The dissolved oxygen concentration is not particularly limited. For example, electroless copper plating solution using ammonium hypophosphite or hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent, electroless nickel-phosphorous plating solution using sodium hypophosphite as a reducing agent Electroless nickel-boron plating solution with dimethylamine borane as reducing agent, electroless palladium plating solution, electroless palladium-phosphorous plating solution with sodium hypophosphite as reducing agent, electroless gold plating solution, electroless silver An electroless plating solution such as an electroless nickel-cobalt-phosphorous plating solution containing sodium hypophosphite as a reducing agent can be used.
After the metal thin film layer is formed, the substrate surface can be brought into contact with a rust preventive agent for rust prevention treatment.

  Usually, thick plating is performed on the metal thin film layer thus obtained to complete the second conductor layer. As thick plating, for example, a pattern-like plating resist is formed on a metal thin film according to a conventional method, and further, plating is grown thereon by wet plating such as electrolytic plating, and then the plating resist is removed. The metal thin film layer is etched into a pattern by etching to form a second conductor layer. Therefore, the second conductor layer is usually composed of a patterned metal thin film layer and plating grown thereon.

Moreover, in this invention, after forming a metal thin film layer or after thick plating, the said metal thin film layer can be heated for the adhesive improvement etc. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C.
Heating may be carried out under pressurized conditions, and as a method of applying pressure at this time, for example, a method of physically applying pressure to the substrate using a hot press machine, a pressurized heating roll machine, or the like is available. Can be mentioned. The applied pressure is usually 0.1 MPa to 20 MPa, preferably 0.5 MPa to 10 MPa. If it is this range, the high adhesiveness of a metal thin film and an electrically insulating layer is securable.

  Further multilayering is possible by repeating the steps A to E in the present invention using the multilayer printed wiring board thus obtained as an inner layer substrate.

  According to the method for producing a multilayer printed wiring board of the present invention, after the hydrophilization treatment in Step B, the conductor layer formed by the plating method can be electrically connected to the conductive layer formed by the plating method even after going through Step C for removing water adhering to the surface of the electrical insulating layer. Sufficient adhesion can be obtained between the insulating layer. In addition, the substrate manufactured by the above method can be used for mounting a semiconductor element such as a CPU and a memory and other mounting parts in an electronic device such as a computer or a mobile phone. In particular, a substrate having fine wiring is suitable as a high-density printed circuit board, as a substrate for a high-speed computer or a portable terminal used in a high-frequency region.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the examples, parts and% are based on weight unless otherwise specified.
The evaluation methods performed in this example are as follows.
(1) Molecular weight (Mw, Mn)
It measured as a polystyrene conversion value by gel permeation chromatography (GPC) using toluene as a solvent.
(2) Hydrogenation rate and maleic anhydride residue content Hydrogenation rate relative to the number of moles of unsaturated bonds in the polymer before hydrogenation (hydrogenation rate) and maleic anhydride relative to the total number of monomer units in the polymer The ratio of the number of moles of acid residues was measured by ¹ H-NMR spectrum.
(3) Glass transfer temperature (Tg)
It measured by the differential scanning calorimetry method (DSC method).

(4) Surface average roughness Ra, surface ten-point average roughness Rzjis
The average roughness Ra and the surface ten-point average roughness Rzjis are both 20 μm × 20 μm rectangles using an optical surface shape measuring device (a color laser microscope trade name “VK-8500” manufactured by Keyence Corporation) that is a non-contact type. It is the value measured for the area.

(6) Evaluation of adhesion The peel strength between the conductor layer and the electrical insulating layer was evaluated by a 90 degree peel strength test according to the peel strength of the copper foil defined in JIS C 6481.

(7) Evaluation of patterning property 50 wiring patterns were formed with a wiring width of 30 μm, a distance between wirings of 30 μm, and a wiring length of 5 cm. Evaluation was made with △ for those without, and X for those with defects.

Example 1
8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] -dodec-3-ene is subjected to ring-opening polymerization, followed by hydrogenation reaction, number average molecular weight (Mn) = 31,200, weight average molecular weight (Mw) = 55,800, Tg = about 140 A hydrogenated polymer at 0 ° C. was obtained. The hydrogenation rate of the obtained polymer was 99% or more.
100 parts of the obtained polymer, 40 parts of maleic anhydride and 5 parts of dicumyl peroxide were dissolved in 250 parts of t-butylbenzene, and reacted at 140 ° C. for 6 hours. The obtained reaction product solution was poured into 1000 parts of isopropyl alcohol to solidify the reaction product to obtain a maleic acid-modified hydrogenated polymer. This modified hydrogenated polymer was vacuum-dried at 100 ° C. for 20 hours. The molecular weight of this modified hydrogenated polymer was Mn = 33,200, Mw = 68,300, and Tg was 170 ° C. The maleic anhydride residue content was 25 mol%.

  100 parts of the modified hydrogenated polymer, 40 parts of bisphenol A bis (propylene glycol glycidyl ether) ether, 5 parts of 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazole and 1 -0.1 part of benzyl-2-phenylimidazole, 10 parts of liquid polybutadiene (trade name “Nisseki Polybutadiene B-1000”, manufactured by Nippon Petrochemical Co., Ltd.) as a polymer soluble in the oxidation treatment liquid, and 215 parts of xylene And it was made to melt | dissolve in the mixed solvent which consists of 54 parts of cyclopentanone, and the varnish of the curable resin composition was obtained.

  The varnish is applied to a polyethylene naphthalate film (support) having a thickness of 40 mm and a surface average roughness Ra of 0.08 μm using a die coater, and then dried at 120 ° C. for 10 minutes in a nitrogen oven. Then, a film-shaped molded product (film-shaped molded product with a support) having a thickness of 35 μm was obtained on the support.

  Double-sided copper-clad substrate with a thickness of 0.8 mm and a square of 150 mm with a wiring width and a distance between wirings of 50 μm, a conductor thickness of 18 μm, and a surface subjected to microetching treatment by contact with an organic acid (glass filler and A core material obtained by impregnating a glass cloth with a varnish containing a halogen-free epoxy resin) is used as an inner layer substrate, and the above-mentioned film-like molded product with a support is cut into a 150 mm square, and the molded product surface is The two-sided copper-clad substrates were superposed on both sides so as to be inside. This was depressurized to 200 Pa using a vacuum laminator provided with heat-resistant rubber press plates at the top and bottom as a primary press, and thermocompression bonded at a temperature of 110 ° C. and a pressure of 0.5 MPa for 60 seconds. Next, using a vacuum laminator with a heat-resistant rubber press plate covered with a metal press plate as a secondary press, the pressure was reduced to 200 Pa and thermocompression bonded at a temperature of 140 ° C. and 1.0 MPa for 60 seconds. Then, the support was peeled off to obtain a resin layer on the inner layer substrate.

Next, the substrate was dipped in an aqueous solution adjusted to 1.0% of 1- (2-aminoethyl) -2-methylimidazole at 30 ° C. for 10 minutes, and then immersed in water at 25 ° C. for 1 minute. After dipping for a minute, the excess solution was removed with an air knife. This was left in a nitrogen oven at 170 ° C. for 60 minutes to cure the resin layer and form an electrically insulating layer on the inner substrate.
In the obtained electrical insulating layer, via-holes with an interlayer connection of 30 μm in diameter were formed using a UV-YAG laser third harmonic to obtain a multilayer substrate with via holes.

  The multilayer substrate with via holes described above was rock-immersed for 10 minutes in a 70 ° C. aqueous solution adjusted to a permanganate concentration of 60 g / liter and a sodium hydroxide concentration of 28 g / liter. Next, the substrate was washed with water by dipping in a water tank for 1 minute and further dipping in another water tank for 1 minute. Subsequently, the substrate was immersed in an aqueous solution at 25 ° C. adjusted to have a hydroxylamine sulfate concentration of 170 g / liter and sulfuric acid of 80 g / liter for 5 minutes, neutralized and reduced, and then washed with water.

  Subsequently, the solution adhering to the multilayer substrate after washing with water was dried at 80 ° C. for 10 minutes in a hot air dryer, and then allowed to stand at room temperature for 30 minutes.

  Next, the multilayer substrate was dipped in an aqueous solution adjusted to 1.0% of 1- (2-aminoethyl) -2-methylimidazole at 60 ° C. for 1 minute and then washed with water.

  As the plating pretreatment, Alcup activator MAT-1-A (manufactured by Uemura Kogyo Co., Ltd.) is 200 ml / liter, and Alcup activator MAT-1-B (manufactured by Uemura Kogyo Co., Ltd.) is 30 ml / liter. Then, it was immersed for 5 minutes in a Pd salt-containing plating catalyst solution at 60 ° C. adjusted so that sodium hydroxide would be 0.35 g / liter. Next, after washing the substrate with the same method as described above, Alcup Deleuther MAB-4-A (manufactured by Uemura Kogyo Co., Ltd.) is 20 ml / liter, Alcup Deyuuser MAB-4-B (manufactured by Uemura Kogyo Co., Ltd.) Was immersed in a solution adjusted to 200 ml / liter at 35 ° C. for 3 minutes to reduce the plating catalyst. Thus, the plating catalyst was adsorbed, and the 10-point average roughness surface 10-point average roughness Rzjis and average roughness Ra of the outermost insulating layer surface of the multilayer substrate subjected to the plating pretreatment were evaluated. The evaluation results are shown in Table 1.

The substrate thus obtained was adjusted so as to be Sulcup PSY-1A (Uemura Kogyo Co., Ltd.) 100 ml / liter, Sulcup PSY-1B (Uemura Kogyo Co., Ltd.) 40 ml / L, formalin 0.2 mol / L. While blowing air into the solution, it was immersed for 5 minutes at a temperature of 36 ° C. to perform electroless copper plating.
The multilayer substrate on which the metal thin film layer was formed by the electroless plating treatment was further washed with water in the same manner as described above, then dried and subjected to rust prevention treatment to obtain a multilayer substrate on which the electroless plating film was formed.

  A dry film of a commercially available photosensitive resist is attached to the surface of the multilayer substrate subjected to the rust prevention treatment by thermocompression bonding, and a mask having a pattern corresponding to the adhesion evaluation pattern is adhered to the dry film. After exposure, development was performed to obtain a resist pattern. Next, it was immersed in a 100 g / liter sulfuric acid solution at 25 ° C. for 1 minute to remove the rust preventive, and electrolytic copper plating was applied to the resist non-formed portion to form an electrolytic copper plating film having a thickness of 18 μm. Next, the resist pattern is stripped and removed with a stripping solution, and an etching process is performed with a cupric chloride and hydrochloric acid mixed solution to form a wiring pattern composed of the metal thin film and the electrolytic copper plating film. A multi-layer circuit board was obtained. Finally, annealing was performed at 170 ° C. for 30 minutes to obtain a multilayer printed wiring board. Evaluation of patterning property and plating adhesion of the obtained multilayer printed wiring board was performed. The evaluation results are shown in Table 1.

Example 2
The same procedure as in Example 1 was performed except that the multilayer substrate washed with water after the neutralization reduction treatment in Example 1 was allowed to stand at room temperature after drying in a hot air dryer for 48 hours. The evaluation results are shown in Table 1.

Comparative Example 1
In Example 1, the multilayer substrate that had been washed with water after the neutralization reduction treatment was dried, and then the operation of immersing the substrate in 1- (2-aminoethyl) -2-methylimidazole was not performed. When carried out in the same manner as in No. 1, the electroless plating was only partially deposited, and partly peeled off during the electrolytic plating. The evaluation results are shown in Table 1.

Comparative Example 2
Example 1 is the same as Example 1 except that the resin layer was cured and an electrical insulating layer was formed on the inner substrate without performing the operation of immersing in 1- (2-aminoethyl) -2-methylimidazole. When electroless plating was carried out in the same manner as above, the electroless plating was only partially deposited, and partly peeled off during the electrolytic plating. The evaluation results are shown in Table 1.

  From the above results, after the hydrophilization treatment, when the conductive layer is formed by plating method by bringing the coordination structure-containing compound into contact with the electrical insulation layer whose surface has been dried, even if the electrical insulation layer is sufficiently dried It has been found that stable adhesion to the second conductor layer formed thereon and good patterning properties can be obtained.

Claims (5)

On the inner layer substrate whose outermost layer is a conductor layer, an uncured or semi-cured resin layer using a curable composition containing an insulating polymer and a curing agent is formed, and this surface is provided with a metal. After contacting a compound having a recognizable structure, the resin layer is cured to form an electrical insulation layer, and then the surface of the electrical insulation layer is hydrophilized, and then the surface of the electrical insulation layer is dried, and further the metal A method for producing a multilayer printed wiring board, comprising contacting a compound having a coordinable structure with a conductive layer after plating. 2. The multilayer print according to claim 1, wherein the hydrophilization treatment is a method in which a solution of an oxidizing compound selected from the group consisting of permanganate, chromate and dichromate is brought into contact with the surface of the electrical insulating layer. A method for manufacturing a wiring board. The method for producing a multilayer printed wiring board according to claim 1, wherein the electrical insulating layer contains a resin and / or filler soluble in the solution of the oxidizing compound. The manufacturing method of the multilayer printed wiring board in any one of Claims 1-3 including the process of heat-processing the metal thin film layer formed in the electrical insulating layer. The multilayer printed wiring board manufactured by the method in any one of Claims 1-4.