JP2008135685A - WIRING BOARD MANUFACTURING METHOD, WIRING BOARD, MULTILAYER WIRING BOARD MANUFACTURING METHOD, AND MULTILAYER WIRING BOARD - Google Patents

Abstract

A method of manufacturing a wiring board capable of manufacturing a wiring board having a high adhesion to the board by applying the damascene method and having excellent high frequency characteristics, and a wiring board obtained by the manufacturing method I will provide a.
(A) a step of forming a recess or a through hole 30 serving as a wiring forming region on one or both surfaces of a substrate; and (B) an electroless plating catalyst or a precursor thereof on the substrate. Forming a polymer layer made of a polymer having a functional group that interacts with the substrate and directly bonding to the substrate surface; (C) applying an electroless plating catalyst or a precursor thereof on the polymer layer; D) Electroless plating to form the metal layer 26, and (E) Wiring is formed by removing unnecessary metal layers on the substrate so that the metal layer remains only in the recesses or through holes. A process for manufacturing the wiring board 36.
[Selection] Figure 2

Description

  The present invention relates to a method for manufacturing a wiring substrate, a method for manufacturing a multilayer wiring substrate, and a wiring substrate or a multilayer wiring substrate obtained by these methods. More specifically, the production of a wiring board that can be applied to the production of a printed wiring board having a high-density wiring used in the field of electronic materials, a wiring board in which wiring layers are laminated via an electrical insulating layer, and the like. The present invention relates to a method, a method for manufacturing a multilayer wiring board, and a wiring board or a multilayer wiring board obtained by these manufacturing methods.

  In recent years, along with demands for higher functionality of electronic devices, etc., the integration of electronic components has increased, and further, high-density mounting has progressed. Miniaturization and high density are progressing. Various methods such as realization of high-definition and stable wiring and adoption of a build-up multilayer wiring board have been studied as measures for increasing the density of printed wiring boards and the like. Furthermore, a product is also available in which wiring layers are laminated by a build-up method in which electrically insulating layers are connected by fine vias.

  Regarding the formation of these fine wirings, “subtractive method” and “semi-additive method” are known as conventional metal pattern forming methods useful in the field of conductive patterns, particularly printed wiring boards. In the subtractive method, a metal layer formed on a substrate is provided with a photosensitive layer (resist film) that is exposed to irradiation with actinic rays, and this photosensitive layer is imagewise exposed and developed to form a resist image. Next, the metal layer is etched to form a metal pattern, and finally the resist is peeled off. In the substrate used in this method, in order to provide adhesion between the substrate and the metal layer, the substrate interface has been subjected to uneven treatment to develop adhesion by the anchor effect. As a result, the substrate interface portion of the resulting metal pattern becomes uneven, and there is a problem in that the high frequency characteristics deteriorate when used as an electrical wiring. Further, since the substrate is required to be processed to form the metal layer, there is a problem that a complicated process of processing the substrate with a strong acid such as chromic acid is necessary. In addition, in order to etch away the metal layer other than the wiring portion using the resist film formed on the wiring (metal layer) as a mask, for example, when isotropic etching is performed, the metal close to the edge portion of the resist film There was a problem that the etching progressed faster in the layer part than in the far part, and the part was further etched, resulting in a state in which the cross-sectional shape of the metal layer was almost trapezoidal (side etching). .

On the other hand, in the semi-additive method, a power supply layer is provided on the surface of the electrically insulating layer by some method, a photosensitive layer that is exposed by irradiation with actinic rays is provided on the power supply layer, imagewise exposed to this photosensitive layer, and developed. Forming a resist image, applying electricity to the power supply layer, performing electroplating, forming a metal wiring in the non-resist existence part, and then etching the power supply layer in the non-metal wiring part to form a metal pattern It is. For the formation of the power feeding layer in this method, a plating method, a sputtering method, a vapor deposition method, or the like is used.
When the power feeding layer is formed by plating, as in the subtractive method, the surface of the electrical insulating layer is processed to have an unevenness in order to provide adhesion between the substrate and the power feeding layer, thereby exhibiting the adhesion by the anchor effect. It was. As a result, the substrate interface portion of the resulting metal pattern becomes uneven, and there is a problem in that the high frequency characteristics deteriorate when used as an electrical wiring. Further, since the substrate is required to be processed to form the metal layer, there is a problem that a complicated process of processing the substrate with a strong acid such as chromic acid is necessary.
In order to provide a power supply layer by sputtering or vapor deposition, a large vacuum facility is required, which is not suitable for manufacturing a multilayer substrate.
When the full additive method or semi-additive method is used, the power supply layer is provided by electroless plating when forming the wiring (metal pattern), so the plating type remaining on the surface of the insulating film has an adverse effect on electromigration. There was a possibility of affecting.

An example of a method for manufacturing a wiring board is a damascene method. In the damascene method, a concave portion or through hole that becomes a wiring formation region is formed in a substrate, and a conductive metal that becomes a wiring material is embedded in the concave portion or through hole by a method such as plating, and then excess conductive metal other than wiring is removed. In this way, the wiring is formed.
For example, in the method for manufacturing a wiring board disclosed in Patent Document 1 below, after forming a groove in a region where a wiring is to be formed by pressing a molded body against a resin substrate, the entire surface of the board is formed. A metal film was formed by electroless copper plating, vapor deposition, or sputtering, and then the metal film was deposited by electrolytic plating using the metal film as a plating power supply layer, and then deposited on the substrate surface outside the wiring formation region. In this method, the metal is removed to form a wiring.
However, in the method as described above, the metal layer (seed layer) formed on the substrate surface by electroless plating or the like is inferior in adhesion to the substrate, so that when the fine wiring is formed, the wiring is dropped from the substrate. There was a problem of doing.
JP 2002-171048 A

The present invention has been made in view of the above-described problems, and an object thereof is to achieve the following object.
That is, the present invention applies a damascene method, suppresses migration, has a wiring with high adhesion to the substrate, and can manufacture a wiring substrate having excellent high frequency characteristics, It aims at providing the wiring board obtained by the manufacturing method.
In addition, the present invention applies a damascene method, suppresses migration, has a wiring with high adhesion to the substrate, and has a high-frequency characteristic, and a method for manufacturing a multilayer wiring substrate, and the manufacturing method. An object of the present invention is to provide a multilayer wiring board.

  As a result of intensive studies, the inventors have formed a polymer layer in which a graft polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof is directly chemically bonded to the substrate, and The inventors have found that the object can be achieved by plating, and have completed the present invention. That is, the means for solving the problems are as follows.

<1> (A) a step of forming a recess or a through-hole serving as a wiring formation region on one surface or both surfaces of the substrate;
(B) forming a polymer layer made of a polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof and directly binding to the substrate surface on the substrate;
(C) providing the electroless plating catalyst or a precursor thereof on the polymer layer;
(D) forming a metal layer by performing electroless plating;
(E) forming a wiring by removing an unnecessary metal layer present on the substrate so that the metal layer remains only in the recess or the through hole;
A method of manufacturing a wiring board, comprising:

  <2> After the step (D), (D ′) the step of forming an electrolytic plating layer by performing electrolytic plating using the metal layer as a seed layer. Production method.

  <3> The step (A) uses a molding material having a surface having a convex portion for forming the concave portion or the through hole, and the surface having the convex portion in the molding material and the substrate are overlapped. The method for producing a wiring board according to <1> or <2>, wherein the process is a step of transferring and forming the through hole or the concave portion on the substrate by applying pressure.

<4> The method for manufacturing a wiring board according to <1> or <2>, wherein the step (A) is a step of forming the recess or the through hole in the substrate by laser light irradiation. .
<5> The wiring substrate according to <1> or <2>, wherein the step (A) is a step of forming the recess or the through hole in the substrate by etching using a photoresist. Manufacturing method.
<6> The method for manufacturing a wiring board according to <1> or <2>, wherein the step (A) is a step of forming the concave portion or the through hole in the substrate by embossing.
<7> The wiring substrate according to <1> or <2>, wherein the step (A) is a step of forming the concave portion or the through hole in the substrate by etching using a metal mask. Manufacturing method.

<8> The method for manufacturing a wiring board according to any one of <1> to <7>, wherein the removal of the plated metal in the step (E) is performed by a polishing process.
<9> The method for manufacturing a wiring board according to any one of <1> to <8>, wherein the removal of the plating metal in the step (E) is performed by etching.

<10> The method for manufacturing a wiring board according to any one of <1> to <9>, wherein a drying step is performed after the step (D) or the step (D ′).
<11> The wiring board according to <1> to <10>, wherein the metal layer formed by the step (D) is a metal layer containing nickel, palladium, molybdenum, or tungsten. Production method.
<12> The electroplating layer formed by the step (D ′) is an electroplating layer containing nickel, cobalt, or chromium. Any one of the above items <1> to <11> The manufacturing method of the wiring board as described in 2 ..

<13> The method for manufacturing a wiring board according to any one of <1> to <12>, wherein the substrate has a surface irregularity of 500 nm or less.
<14>
The method for manufacturing a wiring substrate according to any one of <1> to <12>, wherein the substrate is a substrate having a surface irregularity of 100 nm or less.

<15> The method for producing a wiring board according to <1> to <14>, wherein the adhesion between the substrate and the metal layer is 0.2 kN / m or more.
<16> The wiring board according to any one of <1> to <15>, wherein the board is a board made of an insulating resin having a dielectric loss tangent at 1 GHz of 0.01 or less. Production method.
<17> The wiring board according to any one of <1> to <15>, wherein the board is a board made of an insulating resin having a dielectric constant of 3.5 or less at 1 GHz. Production method.

<18> A wiring board obtained by the method for manufacturing a wiring board according to any one of <1> to <17>.
<19> A multilayer wiring board, wherein two or more wiring boards according to <18> are laminated via an adhesive layer.

<20> (a) A first insulator layer is formed on the wiring formation surface of the wiring board according to the above <18>, and a recess or a through-hole serving as a wiring formation region is formed in the first insulator layer. Process,
(B) forming on the insulator layer a polymer layer made of a polymer having a functional group that interacts with the electroless plating catalyst or a precursor thereof and directly bonding to the substrate surface;
(C) providing an electroless plating catalyst or a precursor thereof on the polymer layer;
(D) performing electroless plating to form a metal layer;
(E) forming a wiring by removing an unnecessary metal layer present on the insulator layer so that the metal layer remains only in the recess or the through hole;
A method for producing a multilayer wiring board, comprising:

<21> (a ′) A second insulator layer is formed on the wiring formation surface after the end of the step (e), and a recess or a through hole serving as a wiring formation region is formed in the second insulator layer. The method for producing a multilayer wiring board according to <20>, wherein the steps (b) to (e) are further performed after performing the steps.
<22> A multilayer wiring board obtained by the method for manufacturing a multilayer wiring board according to any one of <20> or <21>.

According to the present invention, a damascene method is applied to suppress a migration, and a wiring board manufacturing method capable of manufacturing a wiring board having wiring with high adhesion to the board and excellent in high frequency characteristics, and A wiring board obtained by the manufacturing method can be provided.
In addition, according to the present invention, a damascene method is applied to suppress migration, have a wiring with high adhesion to the substrate, and have a high frequency characteristic. The obtained multilayer wiring board can be provided.

[Wiring board manufacturing method and wiring board obtained thereby]
Hereafter, the manufacturing method of the wiring board of this invention is demonstrated in detail.
The method for manufacturing a wiring board according to the present invention includes (A) a step of forming a recess or a through hole serving as a wiring formation region on one or both surfaces of the substrate, and (B) a substrate surface on the substrate. Forming a polymer layer comprising a graft polymer having a functional group that directly binds and interacts with the electroless plating catalyst or a precursor thereof; and (C) an electroless plating catalyst or a precursor thereof on the polymer layer. A step of applying, (D) a step of forming a metal layer by performing electroless plating, and (E) the plating metal deposited by the electrolytic plating only in the recesses or through-holes from the substrate. And a step of forming a wiring by removing the plating metal.

  In the method for manufacturing a wiring board according to the present invention, it is preferable that after the step (D), (D ′) a step of performing electrolytic plating using the metal layer as a seed layer.

Moreover, in the manufacturing method of the wiring board of this invention, it is preferable from a viewpoint of migration suppression that the metal layer formed by the said (D) process is a metal layer containing nickel, palladium, molybdenum, or tungsten. It is an aspect.
Furthermore, it is a preferable aspect that the electrolytic plating layer formed by the step (D ′) that can be carried out after the step (D) is an electrolytic plating layer containing nickel, cobalt, or chromium.

  The wiring board of this invention is a wiring board obtained by the manufacturing method of the wiring board of this invention.

The manufacturing method of the present invention is a method of manufacturing a wiring board to which the damascene method described above is applied. By performing the steps (A) to (E), wiring having high adhesion to the board is provided. In addition, a wiring board (wiring board of the present invention) excellent in high-frequency characteristics can be manufactured. In addition, by applying the damascene method, it is possible to scrape off the plating seed layer that may cause migration and leakage current, and it is also possible to provide a migration-preventing barrier layer. By the substrate manufacturing method, it is possible to obtain a wiring substrate having high insulation reliability between wirings in which migration is effectively prevented.

In addition, according to the method for manufacturing a wiring board of the present invention, a wiring having excellent adhesion to the board can be formed using the damascene method even when the unevenness of the board interface is small.
An example of the smoothness of the substrate used here is a substrate having a surface irregularity of 500 nm or less. That is, according to the method for manufacturing a wiring board of the present invention, on a smooth substrate having a surface irregularity of 500 nm or less, wiring having good adhesion to the substrate, for example, adhesion to the substrate is 0.2 kN / A wiring having a length of m or more can be formed.

  Here, when a polymer layer is formed on a substrate having surface irregularities of 500 nm or less, the surface irregularities of the polymer layer are also 500 nm or less. By applying an electroless plating catalyst or a precursor thereof to such a polymer layer and performing electroless plating, a state in which the plating catalyst and the plating metal enter the polymer layer (composite state) is formed, and The metal layer is also formed on the polymer layer.

The roughness of the substrate interface portion (interface between metal and organic component) of the metal layer thus formed is slightly rough compared to the roughness of the polymer layer surface because the plating catalyst and the plating metal have entered the polymer layer. However, the degree is low. Therefore, plating on the metal layer and unevenness at the interface between the plating catalyst layer (inorganic component) and the polymer layer (organic component) can be suppressed to such an extent that the high-frequency characteristics of the wiring formed according to the present invention do not deteriorate. Therefore, the wiring in the wiring board obtained by the present invention exhibits excellent high frequency characteristics. The high-frequency characteristics are characteristics that reduce transmission loss during high-frequency power transmission, and are characteristics that particularly reduce conductor loss among transmission losses.
Here, if the unevenness of the substrate surface is reduced, the roughness of the substrate interface portion of the metal pattern can be further suppressed, and the high frequency characteristics of the resulting metal pattern are improved. Therefore, in the present invention, the unevenness of the surface is 100 nm or less. It is preferable to use the substrate.

  In the present invention, Rz in JIS B0601, as an indication of this surface irregularity (surface roughness), that is, “the average value of the Z data of the peak from the maximum to the fifth in the designated plane, and the minimum to the fifth “Difference in mean value of valley bottom” is used.

In the method for producing a wiring board according to the present invention, a surface graft layer (polymer) comprising a graft polymer directly bonded to the substrate is subjected to surface graft treatment (details will be described later) on a substrate having a recess or a through-hole serving as a wiring formation region. Layer) is formed. Since the graft polymer constituting the surface graft layer is formed by polymerization from the substrate interface, its mobility is high and it is easy to act on the electroless plating catalyst or its precursor. In addition, due to its high mobility, the electroless plating solution easily penetrates into the film, and the electroless plating proceeds inside or on the surface graft layer. As a result, the substrate interface of the formed metal layer is in a hybrid state with the graft polymer directly bonded to the substrate. For this reason, the unevenness | corrugation of the board | substrate interface of a metal layer is restrained to the minimum, and the metal layer excellent in adhesiveness can be formed according to the said hybrid state. Therefore, it is considered that a wiring formed by further performing electroplating using such a metal layer as a seed layer can form a state in which the wiring layer is in close contact with the substrate in the recess or the through hole.
Hereafter, each process in the manufacturing method of the wiring board of this invention is demonstrated one by one.

<(A) Step of forming a recess or a through-hole serving as a wiring formation region on one surface or both surfaces of the substrate>
In this step, a concave portion or a through hole serving as a wiring formation region is formed on one surface or both surfaces of the substrate. In the wiring formation region formed in this step, either one of the recess and the through hole may be formed, or both the recess and the through hole may be formed.

As a recessed part (groove) formed in this step, the width is preferably about 1 μm to 100 μm, and the depth is preferably 5 μm to 200 μm. The depth of the concave portion can be appropriately set according to the thickness of the wiring to be formed, and the wiring in which the depth of the concave portion is formed in consideration of the removal mode of the unnecessary metal layer in the step (E) described later. The depth of the recess may be 1 μm to 2 μm deeper than the thickness of the wiring to be formed.
The through holes formed in this step preferably have a width in the range of 5 μm to 100 μm.

  Although the formation aspect of the recessed part or through-hole in this process is not specifically limited if it can apply to a damascene method, For example, each formation aspect of the following (1)-(5) is mentioned.

-Formation mode (1)-
Forming mode (1) uses a molding material having a surface provided with a convex part for forming a recess or a through hole, and presses the surface of the molding material provided with the convex part and the substrate, and pressurizes the substrate. In this embodiment, a through hole or a recess is transferred and formed.

  As the molding material used in the formation mode (1), it is desirable to use a material having high hardness and wear resistance. For example, in addition to a material of a metal plate such as nickel or copper, a predetermined hardness and durability are used. A resin material, a ceramic material, etc. provided with A molding material is provided with the convex part for forming a recessed part or a through-hole in a board | substrate. The convex portion can be formed according to the shape of the concave portion or the through hole formed on the substrate by a known method such as a photolithography method.

FIG. 1 is a diagram illustrating an example of a molding material used in the formation mode (1). As shown in FIG. 1, the molding material 10 is configured to have a surface provided with a convex portion 12a for forming a concave portion on the substrate and a convex portion 12b for forming a through hole.
Although the molding material 10 is provided with both the convex part 12a and the convex part 12b, if only a recessed part is formed in a board | substrate, for example, what is necessary is just to provide only the convex part 12a.

  As the step (A), an example of a specific embodiment of the manufacturing method of the present invention to which the formation mode (1) is applied will be described in detail after each step related to the manufacturing method of the wiring board of the present invention is described. .

-Formation mode (2)-
Formation mode (2) is a mode in which a recess or a through hole is formed in the substrate by laser light irradiation. As a laser that can be used in the formation mode (2), for example, a YAG laser, an excimer laser, a CO ₂ laser, or the like can be used.

  Regarding the formation of the recess or the through-hole according to the formation mode (2), for example, WO 04/103039 pamphlet, JP-A 2006-179822, JP-A 2006-165242, JP-A 2004-146742, JP-A 10-256705. And the contents described in each publication such as JP 2004-31710 A can be applied.

-Formation mode (3)-
In the formation mode (3), a recess or a through hole is formed in the substrate by etching using a photoresist. For the formation of the recess or the through hole according to the formation mode (3), for example, the contents described in JP-A-6-125160, JP-A-2005-72166, and the like can be applied.

-Formation mode (4)-
Forming mode (4) is a mode in which the concave portion or the through hole is formed in the substrate by embossing. For the formation of the recess or the through-hole according to this aspect, for example, the contents described in JP-A-2006-147701, JP-A-2005-286295, and the like can be applied.

-Formation mode (5)-
Formation mode (5) is a mode in which a recess or a through hole is formed in the substrate by etching using a metal mask. That is, in this formation mode, a metal pattern serving as a negative mask for forming a recess or a through hole is formed by an additive method or a semi-additive method, and this is used as a metal mask to perform etching on the substrate. It is the aspect which forms a recessed part or a through-hole in this. The metal mask is removed by, for example, CMP after the formation of the recesses or through holes. Moreover, after forming a metal layer by the below-mentioned (B) process-(D) process in the recessed part or through-hole formed by the (A) process, a metal mask has an unnecessary metal layer in (E) process. It may be removed when removed.

  Form (5) is particularly suitable when a resin substrate made of a resin having excellent chemical stability such as a polyimide resin is used as the substrate.

  As an etching method applicable to the formation mode (5), either a wet etching method or a dry etching method may be used. Examples of the wet etching method are described in JP-A-10-195214, JP-A-10-97081, JP-A-2006-310401, JP-A-2003-234558, JP-A-6-209030, and the like. Matters relating to wet etching may be applied. Examples of the dry etching method include gas etching, plasma etching, reactive ion etching (RIE), and the like. For example, the items related to dry etching described in International Publication No. WO01 / 036181 pamphlet are applied. May be.

  The metal mask in the formation mode (5) can also be formed by applying the metal film formation mode described in detail in steps (B) to (D) described later.

  Note that, as the step (A), an example of a specific embodiment of the manufacturing method of the present invention to which the formation mode (5) is applied will be described in detail after describing each step related to the manufacturing method of the wiring board of the present invention. .

  The substrate surface may be smoothed by forming an organic layer on the substrate after forming the recesses or through holes. As the organic layer, for example, a polyimide resin, an epoxy resin, an acrylic resin, or the like often used for a substrate can be used, and a polyimide resin is more preferable.

〔substrate〕
In this step, the substrate on which the recesses and through holes are to be formed will be described in detail.
Examples of the substrate include a glass substrate and a resin substrate. In addition, as a substrate, a composite plate in which an inorganic filler or the like is mixed with a resin material, inorganic fibers such as glass, or cloth made of organic fibers such as polyester, polyamide, and cotton, or a base material such as paper (paper) is made of resin. Adhered substrates, sheets or films (flexible substrates) are also preferably used.

  In the present invention, a resin substrate is particularly preferably used as the substrate. The type of resin substrate is not particularly limited. For example, epoxy resin substrate, phenol resin film, polyimide resin substrate, unsaturated polyester resin substrate, polyester resin substrate, polyphenylene ether resin substrate, polyphenylene sulfide Resin substrates, polyamide resin substrates, cyanate ester resin substrates, benzocyclobutene substrates, liquid crystal polymer films, and the like are preferably used. Moreover, among these, it is preferable that it is a board | substrate containing an epoxy resin, a polyimide resin, or a liquid crystal resin from viewpoints, such as dimensional stability, heat resistance, and electrical insulation.

The substrate made of an insulating resin that can be used in the present invention will be described in more detail.
Examples of the insulating resin for forming a substrate made of an insulating resin include resins such as polyphenylene ether or modified polyphenylene ether, cyanate ester compounds, and epoxy compounds, and a thermosetting resin composition containing at least one of these resins. A substrate formed of a material is preferably used. Preferred combinations when two or more of these resins are combined to form a resin composition include polyphenylene ether or modified polyphenylene ether and cyanate ester compound, polyphenylene ether or modified polyphenylene ether and epoxy compound, polyphenylene ether or modified polyphenylene ether and cyanate. Examples include combinations of ester compounds and epoxy compounds.

  When forming a substrate of a multilayer printed wiring board with such a thermosetting resin composition, it is preferable not to include an inorganic filler selected from the group consisting of silica, talc, aluminum hydroxide, magnesium hydroxide, Moreover, it is preferable that it is a thermosetting resin composition which further contains a bromine compound or a phosphorus compound.

Examples of other insulating resins include 1,2-bis (vinylphenylene) ethane resin or modified resins of this and polyphenylene ether resins. For example, Satoru Amaha et al., “Journal” of Applied Polymer Science, Vol. 92, p1252-1258 (2004).
Furthermore, a liquid crystalline polymer that can be obtained as a commercial product under the name of Kuraray Bexter or a fluororesin typified by polytetrafluoroethylene (PTFE) is also preferred.

Of these resins, fluororesin (PTFE) is most excellent in high frequency characteristics among polymer materials. However, since it is a thermoplastic resin having a low Tg, the dimensional stability against heat is poor, and the mechanical strength is inferior to that of the thermosetting resin material. There is also a problem that the formability and workability are poor. A thermoplastic resin such as polyphenylene ether (PPE) can also be used after being alloyed with a thermosetting resin. For example, it can be used as an alloyed resin of PPE and epoxy resin, triallyl isocyanate, or an alloyed resin of PPE resin introduced with a polymerizable functional group and other thermosetting resins.
Epoxy resins have insufficient dielectric properties as they are, but improvements have been made by the introduction of bulky skeletons. In this way, the introduction and modification of structures that make use of the properties of each resin to compensate for its drawbacks. The resin which performed etc. is used preferably.
For example, cyanate ester is a resin having the most excellent dielectric properties among thermosetting, but is rarely used alone, and is used as a modified resin such as an epoxy resin, a maleimide resin, and a thermoplastic resin. These details are described in “Electronic Technology”, No. 9, 2002, p35, and these descriptions can also be referred to in selecting such an insulating resin.

  In the wiring board obtained by the present invention, from the viewpoint of processing a large amount of data at high speed, it is effective to reduce the dielectric constant and dielectric loss tangent of the board in order to suppress signal delay and attenuation. is there. The use of low dielectric loss tangent material is as described in detail in "Journal of Electronics Packaging Society" Vol. 7, No. 5, P397 (2004), and in particular, an insulating material having low dielectric loss tangent characteristics is adopted. It is preferable to increase the speed. Specifically, the substrate is preferably made of an insulating resin whose dielectric constant (relative dielectric constant) at 1 GHz is 3.5 or less, and from an insulating resin whose dielectric loss tangent at 1 GHz is 0.01 or less. More preferably. The dielectric constant and dielectric loss tangent of the insulating resin are measured using a cavity resonator perturbation method based on a conventional method, for example, the method described in “18th Annual Meeting of the Electronics Packaging Society”, p189. It can be measured using a device (εr for ultra-thin sheet, tan δ measuring device / system, manufactured by Keycom Corporation).

  Thus, in the present invention, it is also useful to select an insulating resin material from the viewpoint of dielectric constant and dielectric loss tangent. Examples of the insulating resin having a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.01 or less include a liquid crystal polymer, a polyimide resin, a fluororesin, a polyphenylene ether resin, a cyanate ester resin, and a bis (bisphenylene) ethane resin. In addition, these modified resins are also included.

[Substrate surface or intermediate layer]
The substrate in the present invention has a surface to which the graft polymer can be directly chemically bonded. In the present invention, the substrate surface itself may have such characteristics, and an intermediate layer having such characteristics may be provided on the substrate surface.

  As the intermediate layer, in particular, when a graft polymer is synthesized by a photograft polymerization method, a plasma irradiation graft polymerization method, or a radiation irradiation graft polymerization method, a layer having an organic surface is preferable. Preferably there is. Organic polymers include epoxy resins, acrylic resins, urethane resins, phenol resins, styrene resins, vinyl resins, polyester resins, polyamide resins, melamine resins, formalin resins and other synthetic resins, gelatin, casein, and cellulose. Any natural resin such as starch can be used. In the photograft polymerization method, plasma irradiation graft polymerization method, radiation irradiation graft polymerization method, etc., since the start of graft polymerization proceeds from the extraction of hydrogen of the organic polymer, polymers that are easy to extract hydrogen, especially acrylic resin, urethane resin, styrene It is particularly preferable from the viewpoint of production suitability to use a resin, vinyl resin, polyester resin, polyamide resin, epoxy resin or the like.

[Layer that exhibits polymerization initiation ability]
In the present invention, from the viewpoint of efficiently generating active sites during graft polymerization, the intermediate layer provided on the substrate surface is a layer containing a compound that exhibits polymerization initiation ability by applying energy (polymerization). It is preferable that it is a layer which expresses initiating ability).
The layer expressing the polymerization initiating ability includes a polymerizable layer containing a polymerizable compound and a polymerization initiator, and a polymer having a functional group having a polymerization initiating ability and a crosslinkable group in the side chain (hereinafter referred to as “specific polymerization initiation” as appropriate. The polymerization initiation layer is obtained by immobilizing the polymer by the crosslinking reaction, and the layers exhibiting the polymerization initiation ability of these two embodiments will be sequentially described.

(Polymerizable layer containing a polymerizable compound and a polymerization initiator)
A polymerizable layer containing a polymerizable compound and a polymerization initiator (hereinafter referred to as “polymerizable layer” as appropriate) dissolves necessary components such as a polymerizable compound and a polymerization initiator in a solvent capable of dissolving them. Then, it can be formed on the substrate surface by a method such as coating, and hardened by heating or light irradiation.

(A) Polymerizable compound The polymerizable compound used in the polymerizable layer has good adhesion to the substrate, and a monomer or polymer having a hydrophilic group can be added by applying energy such as actinic ray irradiation. Although there will be no restriction | limiting in particular if it is a thing, Among these, the hydrophobic polymer which has a polymeric group in a molecule | numerator is preferable.

Specific examples of such hydrophobic polymers include diene homopolymers such as polybutadiene, polyisoprene, and polypentadiene, and allyl groups such as allyl (meth) acrylates and 2-allyloxyethyl methacrylates. Monomer homopolymer;
Furthermore, binary or multicomponent with styrene, (meth) acrylic acid ester, (meth) acrylonitrile, etc. containing diene monomer such as polybutadiene, polyisoprene, polypentadiene or allyl group-containing monomer as a constituent unit. Copolymer;
And linear polymers or three-dimensional polymers having a carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, and high-density polyethylene.

  In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.

  The content of the polymerizable compound is preferably in the range of 0 to 100% by mass and particularly preferably in the range of 10 to 80% by mass in terms of solid content in the polymerizable layer.

(B) Polymerization initiator The polymerizable layer preferably contains a polymerization initiator for expressing the polymerization initiating ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, or the like that can exhibit polymerization initiating ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Can be selected and used as appropriate. Among these, use of photopolymerization having a higher reaction rate (polymerization rate) than thermal polymerization is preferable from the viewpoint of production suitability, and therefore, a photopolymerization initiator is preferably used.

  The photopolymerization initiator is active with respect to the actinic ray to be irradiated, and is capable of polymerizing a polymerizable compound contained in the polymerizable layer and a monomer or polymer having a hydrophilic group. There is no particular limitation, and for example, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator and the like can be used.

  Specific examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Acetophenones such as: benzophenone (4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, ketones; benzoin, benzoin methyl ether, benzoin isopropyl Examples thereof include benzoin ethers such as ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone, and the like.

  The content of the polymerization initiator in the polymerizable layer is preferably in the range of 0.1 to 70% by mass and particularly preferably in the range of 1 to 40% by mass in terms of solid content.

  Examples of the polymerization initiator that can be suitably contained in the polymerizable layer include the following photocationic polymerization initiators and photoradical polymerization initiators.

-Photocationic polymerization initiator-
A photocationic polymerization initiator refers to a compound that generates an acid upon irradiation with actinic rays or radiation to initiate cationic polymerization, and publicly known compounds and mixtures thereof can be appropriately selected and used.

  As the cationic photopolymerization initiator, those listed below can be used singly or in combination of two or more. In this case, the content of the photocationic polymerization initiator is preferably 0.1 to 20% by mass in terms of solid content in the polymerizable layer from the viewpoint of the amount of acid generated, curability, and the like. More preferably, it is in the range of mass%.

  Examples of the photocationic polymerization initiator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, these photocationic polymerization initiators, or compounds obtained by introducing a group or compound having the same action into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. 3914407, JP 63-26653, JP 55-164824, JP 62-69263, JP 63-1446038, JP 63-163452, JP 62-153853 And compounds described in JP-A No. 63-146029 can be used. Further, compounds capable of generating an acid by light as described in US Pat. No. 3,777,778 and European Patent 126712 can also be used.

  As a compound preferable as a photocationic polymerization initiator, the compound represented by the following general formula (b1), (b2), or (b3) can be mentioned.

In general formula (b1), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion, preferably a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ or the following The organic anion which has a carbon atom is preferable.

  Preferable organic anions include organic anions represented by the following formula.

Rc ¹ represents an organic group.
Examples of the organic group in Rc ¹ include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these are a single bond, —O—, —CO ₂ —, —S. _{-, - SO 3 -, -} SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.

Rd ¹ represents a hydrogen atom or an alkyl group. Rc ³ , Rc ⁴ and Rc ⁵ each independently represents an organic group. Preferred examples of the organic group for Rc ³ , Rc ⁴ , and Rc ⁵ include the same organic groups as those for Rc ¹ , and most preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Rc ³ and Rc ⁴ may be bonded to form a ring. Examples of the group formed by combining Rc ³ and Rc ⁴ include an alkylene group and an arylene group. Preferably, it is a C2-C4 perfluoroalkylene group.

As the organic groups of Rc ¹ and Rc ^{3 to} Rc ⁵ , the most preferred is an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved.

The carbon number of the organic group as R ²⁰¹ , R ²⁰² and R ²⁰³ is preferably 1-30, more preferably 1-20.
Two of R ^{201 to} R ²⁰³ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ^{201 to} R ²⁰³ include an alkylene group (eg, butylene group, pentylene group).

Specific examples of the organic group as R ²⁰¹ , R ²⁰² and R ²⁰³ include corresponding groups in the compounds (b1-1), (b1-2) and (b1-3) described later.

In addition, the compound which has two or more structures represented by general formula (b1) may be sufficient. For example, at least one of ^R 201 ^{to R 203} of the compound represented by the general formula (b1) is at least one directly with ^R 201 ^{to R 203} of another compound represented by formula (b1), or, It may be a compound having a structure bonded through a linking group.

  More preferable examples of the compound represented by the general formula (b1) include compounds (b1-1), (b1-2), and (b1-3) described below.

The compound (b1-1) will be described.
Compound (b1-1) is at least one of ^R 201 ^{to R 203} in formula (b1) is an aryl group, an arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R ^{201 to} R ²⁰³ may be an aryl group, or a part of R ^{201 to} R ²⁰³ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, aryldicycloalkylsulfonium compounds, and the like.

  The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

As the alkyl group that the arylsulfonium compound has as necessary, a linear or branched alkyl group having 1 to 15 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, sec -A butyl group, a t-butyl group, etc. can be mentioned.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group and cycloalkyl group of R ^{201 to} R ²⁰³ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and most preferred. Is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of three R ^{201 to} R ²⁰³ , or may be substituted with all three. When R ^{201 to} R ²⁰³ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (b1-2) will be described.
The compound (b1-2) is a compound when R ^{201 to} R ²⁰³ in the general formula (b1) each independently represents an organic group not containing an aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group not containing an aromatic ring as R ^{201 to} R ²⁰³ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
R ^{201 to} R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear, branched or cyclic 2-oxoalkyl group, an alkoxycarbonylmethyl group, particularly A linear or branched 2-oxoalkyl group is preferred.

The alkyl group as R ^{201 to} R ²⁰³ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, pentyl group), and a linear or branched 2-oxoalkyl group or alkoxycarbonylmethyl group is more preferable.

The cycloalkyl group as R ^{201 to} R ²⁰³ preferably includes a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group), and a cyclic 2-oxoalkyl group is more preferable.

Preferred examples of the linear, branched and cyclic 2-oxoalkyl group represented by R ^{201 to} R ²⁰³ include a group having> C═O at the 2-position of the above alkyl group or cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group as R ^{201 to} R ²⁰³ is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R ^{201 to} R ²⁰³ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the compound (b1-3) will be described.
The compound (b1-3) is a compound represented by the following general formula (b1-3), and is a compound having a phenacylsulfonium salt structure.

In General Formula (b1-3), R ^{1c to} R ^5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom. R ^6c and R ^7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R ^x and R ^y each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group. Any two or more of R ^{1c to} R ^5c , R ^6c and R ^7c , and R ^x and R ^y may be bonded to each other to form a ring structure. Zc ^- represents a non-nucleophilic anion, in the general formula (b1) X ^- can be the same as the non-nucleophilic anion.

The alkyl group as R ^{1c to} R ^7c may be either linear or branched, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (for example, Methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).

Preferred examples of the cycloalkyl group represented by R ^{1c to} R ^7c include cycloalkyl groups having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).

The alkoxy group as R ^{1c to} R ^{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. Group (for example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), cyclic alkoxy group having 3 to 8 carbon atoms (for example, cyclopentyloxy group) Cyclohexyloxy group).

Examples of the group formed by combining any two or more of R ^{1c to} R ^5c , R ^6c and R ^7c , and R ^x and R ^y include a butylene group and a pentylene group. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond.

Preferably any one of R ^{1c to} R ^5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R ^{1c to} R ^5c is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

^Examples of the alkyl group and cycloalkyl group as R ^x and R ^y include the same alkyl groups and cycloalkyl groups as R ^{1c to} R ^7c .
R ^x and R ^y are preferably a 2-oxoalkyl group or an alkoxycarbonylmethyl group.
Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R ^{1c to} R ^5c .
The alkoxy group in the alkoxycarbonylmethyl group may be the same as the alkoxy group as R ^1c to R ^5c.

R ^x and R ^y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

Formula (b2), in the formula ^{(b3), R} 204 ~R ²⁰⁷ each independently represents an aryl group, an alkyl group or a cycloalkyl group. X ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of X ^{− in} formula (b1).

The aryl group for R ^{204 to} R ²⁰⁷ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
The alkyl group as R ^{204 to} R ²⁰⁷ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, pentyl group). The cycloalkyl group as R ²⁰⁴ to R ²⁰⁷ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
The R ²⁰⁴ to R ²⁰⁷ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.

  Examples of the photocationic polymerization initiator that may be used further include compounds represented by the following general formula (b4), general formula (b5), or general formula (b6).

In general formulas (b4) to (b6), Ar ³ and Ar ⁴ each independently represents an aryl group. R ²⁰⁶ , R ²⁰⁷ and R ²⁰⁸ each independently represents an alkyl group, a cycloalkyl group or an aryl group. A represents an alkylene group, an alkenylene group or an arylene group.

  Preferred among the cationic photopolymerization initiators are compounds represented by general formulas (b1) to (b3).

  Specific examples of the particularly preferable photocationic polymerization initiator [Exemplary compounds (b-1) to (b-61)] are listed below, but the present invention is not limited thereto.

  In addition, oxazole derivatives and s-triazine derivatives described in paragraphs [0029] to [0030] of JP-A-2002-122994 are also preferably used. Onium salt compounds and sulfonate compounds exemplified in paragraphs [0037] to [0063] of JP-A No. 2002-122994 can also be suitably used in the present invention.

-Photo radical polymerization initiator-
The radical photopolymerization initiator may be a low molecule or a polymer.
Specific examples of the low-molecular photoradical polymerization initiator include acetophenones, hydroxyalkylphenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram monosulfide, trichloro Known radical generators such as methyltriazine and thioxanthone can be used. In addition, since sulfonium salts and iodonium salts that are usually used as photoacid generators also act as radical generators upon irradiation with light, they may be used in the present invention.

  Examples of the polymer photoradical polymerization initiator include JP-A-9-77891, JP-A-10-45927, Japanese Patent Application No. 2006-053430, Japanese Patent Application No. 2006-264706, Photochemistry & Photobiology, Vol. 5, high molecular compounds having an active carbonyl group, trichloromethyltriazine, or thioxanthone in the side chain, as described in JP-A-5, p46 (1999). Examples of the polymer radical polymerization initiator include the following compounds (1) to (14).

  The radical photopolymerization initiator is preferably a polymer radical photopolymerization initiator from the viewpoint of graft polymerizability. The weight average molecular weight of the polymer type radical photopolymerization initiator is preferably 10,000 or more, more preferably 30000 or more. The upper limit of the weight average molecular weight is preferably 100,000 from the viewpoint of solubility.

  Further, when the polymerizable compound contained in the polymerizable layer is an epoxy resin, a polymer type radical photopolymerization initiator may also serve as the epoxy resin. As such a polymer-type photoradical polymerization initiator, compounds represented by the following (15) to (30) can be suitably used. Here, in (15) to (30), x and y represent mole fractions, and x + y = 100 (x ≠ 0, y ≠ 0).

  When the above-mentioned radical photopolymerization initiator is used, the content thereof is such that the graft polymerizability, the point of suppressing the decrease in adhesion strength resulting therefrom, the point of suppressing the decrease in Tg of the cured product, and the dielectric constant of the cured product are increased. From the point of preventing the problems on the thermal characteristics and electrical characteristics, it is preferably about 0.1 to 50% by mass, and about 1.0 to 30.0% by mass with respect to the total solid content. More preferred.

The solvent used when applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount when the polymerizable layer is formed on the substrate is 0.1 in terms of the mass after drying from the viewpoint of sufficient polymerization initiation ability and prevention of film peeling while maintaining film properties. -20 g / m ² is preferable, and 1-15 g / m ² is more preferable.

As described above, the polymerizable layer forming composition is disposed on the substrate surface by coating or the like, and the solvent is removed to form a polymerizable layer to form a polymerizable layer. Or it is preferable to harden by light irradiation. In particular, if the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is cured to some extent in advance, so that the polymerizable layer drops off after the graft polymer is formed on the substrate. This is preferable because the situation can be effectively suppressed. Here, the reason why light irradiation is used for pre-curing is the same as described in the section of the photopolymerization initiator.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried. However, from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C. It is more preferable to select heating conditions within a drying time of 10 minutes.

  Light irradiation performed as desired after heat drying includes, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp as a light source. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used. From the viewpoint of not inhibiting the subsequent formation of the graft pattern and the formation of the bond between the active site of the polymerizable layer and the graft chain, which is performed by applying energy, the polymerizable compound present in the polymerizable layer is partially Even after radical polymerization, it is preferable to irradiate with light to such an extent that radical polymerization does not occur completely, and the light irradiation time varies depending on the intensity of the light source, but is generally preferably within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent washing is 10% or more and the initiator remaining rate after pre-curing is 1% or more.

(Polymerization initiation layer formed by immobilizing a specific polymerization initiation polymer by a crosslinking reaction)
The polymerization initiating layer in the present invention may include a specific polymerization initiating polymer. This specific polymerization initiating polymer is a polymer having a functional group having a polymerization initiating ability and a crosslinkable group in the side chain. For this reason, in the specific polymerization initiating polymer, it is possible to form a polymerization initiating layer in a form in which the polymerization initiating group is bonded to the polymer chain and the polymer chain is fixed by a crosslinking reaction. When a graft polymer is generated on the surface of such a polymerization initiating layer, for example, even if a solution containing a monomer having a hydrophilic group is brought into contact, the initiator component in the polymerization initiating layer is eluted in the solution. Can be prevented. Further, when forming the polymerization initiating layer, not only a normal radical crosslinking reaction but also a condensation reaction or an addition reaction between polar groups can be used, so that a stronger crosslinking structure can be obtained. As a result, it is possible to more efficiently prevent the initiator component in the polymerization initiation layer from eluting, and by suppressing the by-production of a homopolymer not directly bonded to the surface of the polymerization initiation layer, the polymerization initiation layer Only the graft polymer directly bonded to the surface is produced.

  Specific polymerization initiating polymers used here include those described in paragraphs [0011] to [0158] of JP-A No. 2004-161995. Specific examples of particularly preferred specific polymerization initiating polymers include the following.

-Formation of polymerization initiation layer-
In the polymerization initiation layer of the present invention, the above-mentioned specific polymerization initiation polymer is dissolved in an appropriate solvent, a coating solution is prepared, the coating solution is disposed on the substrate by coating, the solvent is removed, and the crosslinking reaction proceeds. To form a film. That is, the specific polymerization initiating polymer is immobilized by the progress of the crosslinking reaction. The immobilization by the crosslinking reaction includes a method using a self-condensation reaction of a specific polymerization initiating polymer and a method using a crosslinking agent in combination, and a crosslinking agent is preferably used. As a method of using the self-condensation reaction of the specific polymerization initiating polymer, for example, when the crosslinkable group is —NCO, the method uses the property that the self-condensation reaction proceeds by applying heat. As this self-condensation reaction proceeds, a crosslinked structure can be formed.

Moreover, as a crosslinking agent used for the method of using a crosslinking agent together, a conventionally well-known thing as described in Shinji Yamashita "crosslinking agent handbook" can be used.
Preferred combinations of the crosslinkable group and the crosslinker in the specific polymerization initiating polymer include (crosslinkable group, crosslinker) = (— COOH, polyvalent amine), (—COOH, polyvalent aziridine), (—COOH, Polyvalent isocyanate), (—COOH, polyvalent epoxy), (—NH ₂ , polyvalent isocyanate), (—NH ₂ , aldehydes), (—NCO, polyvalent amine), (—NCO, polyvalent isocyanate) , (—NCO, polyhydric alcohol), (—NCO, polyhydric epoxy), (—OH, polyhydric alcohol), (—OH, polyhalogenated compound), (—OH, polyhydric amine), (− OH, acid anhydride). Among these, (functional group, cross-linking agent) = (— OH, polyvalent isocyanate) is a more preferable combination in that a urethane bond is formed after the cross-linking and a high-strength cross-linking can be formed.

  Specific examples of the crosslinking agent in the present invention include the structures shown below.

  Such a crosslinking agent is added to the coating solution containing the above-mentioned specific polymerization initiating polymer when the polymerization initiating layer is formed. Thereafter, the crosslinking reaction proceeds by the heat during the drying of the coating film, and a strong crosslinked structure can be formed. More specifically, the following ex1. Or the dehydration reaction indicated by ex2. The cross-linking reaction proceeds by the addition reaction represented by the above, and a cross-linked structure is formed. The temperature conditions in these reactions are preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 80 ° C. or higher and 200 ° C. or lower.

  The amount of the crosslinking agent added in the coating solution varies depending on the amount of the crosslinkable group introduced into the specific polymerization initiating polymer, but the degree of crosslinking and the polymerization reaction due to the remaining unreacted crosslinking component remain. From the viewpoint of influence, it is usually preferably 0.01 to 50 equivalents, more preferably 0.01 to 10 equivalents, and 0.5 to 3 equivalents relative to the number of moles of the crosslinkable group. Is more preferable.

Moreover, the solvent used when apply | coating a polymerization start layer will not be restrict | limited especially if the above-mentioned specific polymerization start polymer melt | dissolves. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by weight.

The coating amount of the polymerization initiation layer is or initiating ability of surface graft polymerization, in view of film properties, the weight after drying is preferably 0.1 to 20 g / m ^2, further preferably 1 to 15 g / m ^2.

In the present invention, a substrate comprising a polyimide having a polymerization initiation site in the skeleton as shown below (hereinafter, appropriately referred to as a specific polyimide) is used without using the polymerization initiation layer as described above. You can also
The substrate comprising this specific polyimide is prepared as a polyimide precursor compound, and after this polyimide precursor compound is molded into a desired substrate shape, heat treatment is performed to change the polyimide precursor into a polyimide structure (specific polyimide). It can produce.

  Although the specific example of the specific polyimide produced as mentioned above is shown, it is not limited to these.

  The unevenness of the substrate surface applied to the present invention is preferably 500 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, and most preferably 20 nm or less. The unevenness on the surface of the substrate is preferable when the obtained metal film is used as wiring or the like, as the surface unevenness becomes smaller, the electrical loss during high-frequency power transmission decreases.

-Step of forming a barrier layer-
The method for manufacturing a wiring board of the present invention includes a step of forming a barrier layer simultaneously with the step (A) or after the completion of the step (A) and before the step (B) described later. Also good. By forming the barrier layer, it is possible to effectively prevent a decrease in insulation reliability due to migration of metal atoms in the wiring formed in the present invention.

  (A) In the case of performing the step of forming the barrier layer simultaneously with the step, for example, in the above-described formation mode (1) of the concave portion or the through hole, the component constituting the barrier layer on the surface provided with the convex portion in the molding And a barrier layer is formed simultaneously with the formation of the recess or the through hole.

  In the case of performing the step of forming the barrier layer after the completion of the step (A) and before performing the step (B) described later, for example, a composition containing a component constituting the barrier layer is formed into a recess or Examples include an aspect in which coating is performed on a substrate in which through holes are formed, and a mode in which components constituting the barrier layer are vapor-deposited on a substrate in which recesses or through holes are formed by a vapor phase method or the like.

About the material which comprises a barrier layer, its formation method, etc., it describes in each gazette, such as Unexamined-Japanese-Patent No. 11-45887, Unexamined-Japanese-Patent No. 2000-223491, Unexamined-Japanese-Patent No. 2001-85438, Unexamined-Japanese-Patent No. 2001-110751, etc., for example. The matters to be applied can also be applied to the present invention.
The barrier layer may be an alloy layer including a plurality of metals.

<(B) Step of forming a polymer layer made of a graft polymer having a functional group that directly binds to the substrate surface and interacts with the electroless plating catalyst or its precursor> on the substrate>
In this step, the surface of the substrate having a functional group that interacts with the electroless plating catalyst or its precursor on the substrate on which the recesses and / or through-holes serving as the wiring formation regions are formed by the step (A). A polymer layer composed of a polymer directly bonded to is formed.

(Surface graft polymerization)
In this step, a polymer layer is formed using a means generally called surface graft polymerization.
Graft polymerization is a method of synthesizing a graft (grafting) polymer by giving an active species on a highly polarizable base compound chain, thereby further polymerizing another monomer for initiating the polymerization, When the provided polymer compound forms a solid surface, it is called surface graft polymerization.

In the present invention, the substrate is formed by bringing a compound having a polymerizable group and an interactive group into contact with the surface of the substrate on which the concave portions or through-holes to be the wiring formation regions described above are formed, and applying energy. An active site is generated on the surface, the active site reacts with the polymerizable group of the compound and the substrate to cause a surface graft polymerization reaction.
This contact may be performed by immersing the substrate in a liquid composition containing the compound having a polymerizable group and an interactive group. However, from the viewpoint of handleability and production efficiency, it will be described later. Thus, it is preferable to form the layer which has as a main component the composition containing the compound which has this polymeric group and interactive group on a substrate surface by the apply | coating method.

  In addition, the contact between the compound having a polymerizable group and an interactive group and the substrate surface is a case where the formation mode (1) is applied when forming the recess or the through hole in the step (A). Using a liquid composition containing a compound having a polymerizable group and an interactive group on the surface having a convex portion of the molding material, the contact is performed simultaneously with the formation of the concave portion or the through hole. You can also.

(Compound having a polymerizable group and an interactive group)
The compound having a polymerizable group and an interactive group used in the present invention is obtained by using at least one selected from a monomer having an interactive group, a macromonomer, or a monomer having an interactive group, which will be described later. Polymers in which an ethylene addition polymerizable unsaturated group (polymerizable group) such as a vinyl group, an allyl group, or a (meth) acryl group is introduced as a polymerizable group in the homopolymer or copolymer to be obtained can be mentioned. The polymer has a polymerizable group at least at a terminal or a side chain.

-Monomers and macromonomers having interactive groups-
As the monomer that can be used, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, styrene sulfonate, and the like can be used. Specifically, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or a hydrohalide thereof, 3-vinylpropionic acid Or alkali metal salts and amine salts thereof, vinylsulfonic acid or alkali metal salts and amine salts thereof, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, Acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, N-vinylpyrrolidone (the following structure), sodium styrenesulfonate, vinylbenzoic acid, etc. carboxyl group, sulfonic acid group, phosphoric acid group, amino Group or their salts, hydroxyl group, amido group, phosphine group, imidazole group, pyridine group, or their salts, and a monomer having a functional group such as ether group can be used.

  As an example of a compound having a polymerizable group and an interactive group, a macromonomer can also be used. As a method for producing the macromonomer used in this case, for example, Chapter 2 “Macromonomer” of “Macromonomer Chemistry and Industry” (editor Yuya Yamashita) published on September 20, 1999, published by IPC Publishing Bureau. Various production methods have been proposed in "Synthesis of". Particularly useful macromonomers that can be used include macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylstyrene sulfonic acid, and salts thereof Sulfonic acid macromonomer derived from the above monomers, (meth) acrylamide, N-vinylacetamide, N-vinylformamide, amide macromonomer derived from N-vinylcarboxylic acid amide monomer, hydroxyethyl methacrylate, hydroxy Macromonomers derived from hydroxyl group-containing monomers such as ethyl acrylate and glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol acrylate DOO macromonomers derived from alkoxy group or ethylene oxide group-containing monomers such as. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromonomer used in this embodiment. In these macromonomers, useful weight average molecular weights are in the range of 250 to 100,000, with a particularly preferred range being 400 to 30,000.

-Polymer having polymerizable group and interacting group-
A polymer having a polymerizable group and an interactive group can be synthesized as follows.
As synthesis methods, i) a method in which a monomer having an interactive group and a monomer having a polymerizable group are copolymerized, and ii) a monomer having an interactive group and a monomer having a double bond precursor are copolymerized. And a method of introducing a double bond by treatment with a base or the like, and iii) a method of reacting a polymer having an interactive group with a monomer having a polymerizable group. From the viewpoint of synthesis suitability, iii) a method of introducing a polymerizable group by reacting a polymer having an interactive group with a monomer having a polymerizable group, and ii) a monomer having an interactive group And a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like.

  In the above method iii), the monomer having an interactive group used for the synthesis of a polymer having a polymerizable group and an interactive group is (meth) acrylic acid or an alkali metal salt and amine salt thereof, itaconic acid. Or alkali metal salts and amine salts thereof, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or a hydrohalide thereof, 3 -Vinyl propionic acid or its alkali metal salt and amine salt, vinyl sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpro Sulfonic acid, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, N-vinylpyrrolidone (the following structure), carboxyl group, sulfonic acid group, phosphoric acid group, amino group, or salts thereof, hydroxyl group, amide group , A phosphine group, an imidazole group, a pyridine group, or a salt thereof, and a monomer having a functional group such as an ether group.

In addition, examples of the monomer having a polymerizable group that is copolymerized with a monomer having an interactive group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Monomer having a polymerizable group used for introducing an unsaturated group by reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group and an epoxy group in a polymer having an interactive group As (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isocyanatoethyl (meth) acrylate, and the like.

  Next, ii) a method of copolymerizing a monomer having an interactive group and a monomer having a double bond precursor and then introducing a double bond by treatment with a base or the like will be described in detail. Regarding this synthesis method, the method described in JP-A No. 2003-335814 can be used. As the monomer having a double bond precursor, compounds (i-1 to i-60) described in JP-A-2003-335814 can be used, and among these, the following (i-1) is particularly preferable.

Furthermore, polymerization used to introduce unsaturated groups by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group, and an epoxy group in a polymer having an interactive group Examples of the monomer having a functional group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.
ii) Regarding a method of introducing a double bond by treatment with a base after copolymerizing a monomer having an interactive group and a monomer having a double bond precursor, for example, JP-A-2003-335814 The technique described in the publication can be used.

  In the present invention, the polymer compound having a polymerizable group and an interactive group includes a polymer having a cyano group as an interactive group (hereinafter referred to as “cyano group-containing” from the viewpoint of improving the insulation reliability between wirings. Can be suitably used.

  The cyano group-containing polymerizable polymer in the present invention is preferably a copolymer including, for example, a unit represented by the following formula (1) and a unit represented by the following formula (2).

In the above formulas (1) and (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z are each independently A single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group; L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group; To express.

When R ^{1 to} R ⁵ are substituted or unsubstituted alkyl groups, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the substituted alkyl group include methoxy And a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, and the like.
R ¹ is preferably a hydrogen atom, a methyl group, a hydroxy group, or a methyl group substituted with a bromine atom.
R ² is preferably a hydrogen atom, a methyl group, a hydroxy group, or a methyl group substituted with a bromine atom.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom or a methyl group.

When X, Y and Z are a substituted or unsubstituted divalent organic group, the divalent organic group includes a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group. Is mentioned.
As the substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, or these groups are substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like. Those are preferred.
The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like.
Among _{them, - (CH 2) n -} (n is an integer of 1 to 3) are preferred, more preferably -CH ₂ -.

L ¹ is preferably a divalent organic group having a urethane bond or a urea bond, and among them, those having a total carbon number of 1 to 9 are preferable. Incidentally, the total number of carbon atoms of L ^1, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^1.
More specifically, the structure of L ¹ is preferably a structure represented by the following formula (1-1) or formula (1-2).

In the above formula (1-1) and formula (1-2), R ^a and R ^b each independently represent a substituted or unsubstituted methylene group, ethylene group, propylene group, or butylene group.

L ² is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these. The group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group. Among them, L ² preferably has 1 to 15 total carbon atoms, and particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L ^2, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^2.
Specifically, methylene group, ethylene group, propylene group, butylene group, phenylene group, and those groups substituted with methoxy group, hydroxy group, chlorine atom, bromine atom, fluorine atom, etc., The group which combined these is mentioned.

  As the cyano group-containing polymerizable polymer in the present invention, the unit represented by the formula (1) is preferably a unit represented by the following formula (3).

In the above formula (3), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and Z is a single bond, a substituted or unsubstituted divalent organic group. Represents an ester group, an amide group, or an ether group, W represents a nitrogen atom or an oxygen atom, and L ¹ represents a substituted or unsubstituted divalent organic group.

^{R 1} and ^{R 2} in Formula (3), the formula (1) has the same meaning as ^{R 1} or ^{R 2} in, are the preferable examples.

Z in formula (3) has the same meaning as Z in formula (1), and the preferred examples are also the same.
Further, ^{L 1} in the formula (3) also has the same meaning as ^{L 1} in Formula (1), and preferred examples are also the same.

  As the cyano group-containing polymerizable polymer in the present invention, the unit represented by the formula (3) is preferably a unit represented by the following formula (4).

In formula (4), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and V and W each independently represent a nitrogen atom or an oxygen atom. , L ¹ represents a substituted or unsubstituted divalent organic group.

^{R 1} and ^{R 2} in the formula (4), the formula (1) have the same meanings as ^{R 1} and ^{R 2} in, and so are the preferable examples.

L ¹ in Formula (4) has the same meaning as L ¹ in Formula (1), and the preferred examples are also the same.

In the formulas (3) and (4), W is preferably an oxygen atom.
In Formulas (3) and (4), L ¹ is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, and among these, the total number of carbon atoms is 1 to 9. Are particularly preferred.

  Moreover, as a cyano group containing polymeric polymer in this invention, it is preferable that the unit represented by said Formula (2) is a unit represented by following formula (5).

In the above formula (5), R ² represents a hydrogen atom or a substituted or unsubstituted alkyl group, U represents a nitrogen atom or an oxygen atom, and L ² represents a substituted or unsubstituted divalent organic group. Represents a group.

R ² in Formula (5) has the same meaning as R ¹ and R ² in Formula (1), and is preferably a hydrogen atom.

L ² in formula (5) has the same meaning as L ² in formula (1), and is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these. .
In particular, in Formula (5), L ² is preferably a divalent organic group having a linear, branched, or cyclic alkylene group at the site of connection with the cyano group. The organic group preferably has 1 to 10 carbon atoms.
In another preferred embodiment, L ² in Formula (5) is preferably a divalent organic group having an aromatic group at the site of connection with the cyano group. Among these, the divalent organic group is preferred. However, it is preferable that it is C6-C15.

The cyano group-containing polymerizable polymer in the present invention includes a unit represented by the above formulas (1) to (5), and is a polymer having a polymerizable group and a cyano group in the side chain. is there.
This cyano group-containing polymerizable polymer can be synthesized, for example, as follows.

Examples of the polymerization reaction include radical polymerization, cationic polymerization, and anionic polymerization. From the viewpoint of reaction control, radical polymerization or cationic polymerization is preferably used.
The cyano group-containing polymerizable polymer in the present invention includes: 1) a case where a polymerization form forming a polymer main chain is different from a polymerization form of a polymerizable group introduced into a side chain; and 2) a polymerization form forming a polymer main chain. And the synthesis method of the polymerizable group introduced into the side chain is different in the synthesis method.

1) When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain 1-1) An embodiment in which the polymer main chain is formed by cationic polymerization and the polymerization form of the polymerizable group introduced into the side chain is radical polymerization, and 1-2) the polymer main chain is formed by radical polymerization. There is a mode in which the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization.

1-1) A mode in which polymer main chain formation is performed by cationic polymerization, and a polymerization form of a polymerizable group introduced into a side chain is radical polymerization. In the present invention, polymer main chain formation is performed by cationic polymerization, and a side chain is formed. Examples of the monomer used in an embodiment in which the polymerization form of the polymerizable group introduced into the radical polymerization is radical polymerization include the following compounds.

-Monomers used to form polymerizable group-containing units As monomers used to form polymerizable group-containing units used in this embodiment, vinyl (meth) acrylate, allyl (meth) acrylate, 4- ( (Meth) acryloylbutane vinyl ether, 2- (meth) acryloylethane vinyl ether, 3- (meth) acryloylpropane vinyl ether, (meth) acryloyloxydiethylene glycol vinyl ether, (meth) acryloyloxytriethylene glycol vinyl ether, (meth) acryloyl 1st ter Pioneer, 1- (meth) acryloyloxy-2-methyl-2-propene, 1- (meth) acryloyloxy-3-methyl-3-butene, 3-methylene-2- (meth) acryloyloxy-norbornane, 4,4′-ethylidene diphenol di (meth) acrylate, methacrolein di (meth) acryloyl acetal, p-((meth) acryloylmethyl) styrene, allyl (meth) acrylate, 2- (bromomethyl) vinyl acrylate, 2- (Hydroxymethyl) allyl acrylate and the like.

Monomers used to form cyano group-containing units Monomers used to form cyano group-containing units used in this embodiment include 2-cyanoethyl vinyl ether, cyanomethyl vinyl ether, 3-cyanopropyl vinyl ether, 4-cyanobutyl Vinyl ether, 1- (p-cyanophenoxy) -2-vinyloxy-ethane, 1- (o-cyanophenoxy) -2-vinyloxy-ethane, 1- (m-cyanophenoxy) -2-vinyloxy-ethane, 1- ( p-cyanophenoxy) -3-vinyloxy-propane, 1- (p-cyanophenoxy) -4-vinyloxy-butane, o-cyanobenzyl vinyl ether, m-cyanobenzyl vinyl ether, p-cyanobenzyl vinyl ether, allyl cyanide, allyl cyanoacetic acid And the following compounds.

Polymerization methods include general cation polymerization methods described in Experimental Chemistry Course “Polymer Chemistry”, Chapter 2-4 (p74) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu, Chapter 7 (p195). Can be used. In the cationic polymerization, proton acids, metal halides, organometallic compounds, organic salts, metal oxides and solid acids, and halogens can be used as initiators. As possible initiators, the use of metal halides and organometallic compounds is preferred.
Specifically, boron trifluoride, boron trichloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, tin bromide, phosphorus pentafluoride, antimony chloride, molybdenum chloride, tungsten chloride, iron chloride, Examples include dichloroethylaluminum, chlorodiethylaluminum, dichloromethylaluminum, chlorodimethylaluminum, trimethylaluminum, trimethylzinc, and methylgrineer.

1-2) A mode in which polymer main chain formation is performed by radical polymerization and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization In the present invention, polymer main chain formation is performed by radical polymerization, and the side chain Examples of the monomer used in an embodiment in which the polymerization form of the polymerizable group introduced into is cationic polymerization include the following compounds.

-Monomer used for forming polymerizable group-containing unit The same monomers as those used for forming the polymerizable group-containing unit mentioned in the embodiment 1-1) can be used.

Monomers used to form cyano group-containing units Monomers used to form cyano group-containing units used in this embodiment include cyanomethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 3-cyanopropyl ( (Meth) acrylate, 2-cyanopropyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 4-cyanobutyl (meth) acrylate, 5-cyanopentyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, 7-cyano Hexyl (meth) acrylate, 8-cyanohexyl (meth) acrylate, 2-cyanoethyl- (3- (bromomethyl) acrylate), 2-cyanoethyl- (3- (hydroxymethyl) acrylate), p-cyanophenyl (meth) ) Acrylate, o-cyanophenyl (meth) acrylate, m-cyanophenyl (meth) acrylate, 5- (meth) acryloyl-2-carbonitryl-norbornene, 6- (meth) acryloyl-2-carbonitryl-norbornene, 1 -Cyano-1- (meth) acryloyl-cyclohexane, 1,1-dimethyl-1-cyano- (meth) acrylate, 1-dimethyl-1-ethyl-1-cyano- (meth) acrylate, o-cyanobenzyl (meta ) Acrylate, m-cyanobenzyl (meth) acrylate, p-cyanobenzyl (meth) acrylate, 1-cyanocycloheptyl acrylate, 2-cyanophenyl acrylate, 3-cyanophenyl acrylate, vinyl cyanoacetate, 1-cyano-1- Cyclopropanecarboxylic acid vinyl , Allyl cyanoacetate, allyl 1-cyano-1-cyclopropanecarboxylate, N, N-dicyanomethyl (meth) acrylamide, N-cyanophenyl (meth) acrylamide, allyl cyanomethyl ether, allyl-o-cyanoethyl ether, allyl -M-cyanobenzyl ether, allyl-p-cyanobenzyl ether and the like.
A monomer having a structure in which a part of hydrogen of the monomer is substituted with a hydroxyl group, an alkoxy group, a halogen, a cyano group, or the like can also be used.

Polymerization methods include general radical polymerization methods described in Experimental Chemistry Course “Polymer Chemistry” Chapter 2-2 (p34) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu Chapter 5 (p125). Can be used. As the initiator for radical polymerization, a high-temperature initiator that requires heating at 100 ° C. or higher, a normal initiator that starts by heating at 40 to 100 ° C., a redox initiator that starts at a very low temperature, and the like are known. In general, an initiator is preferred from the viewpoint of stability of the initiator and ease of handling of the polymerization reaction.
Usual initiators include benzoyl peroxide, lauroyl peroxide, peroxodisulfate, azobisisobutyronitrile, azovir-2,4-dimethylvaleronitrile.

2) When the polymerization form forming the polymer main chain is the same as the polymerization form of the polymerizable group introduced into the side chain Polymerization form forming the polymer main chain and the polymerization form of the polymerizable group introduced into the side chain Are the same, 2-1) both are cationic polymerization, and 2-2) both are radical polymerization.

2-1) Both are aspects of cationic polymerization In both aspects of cationic polymerization, as the monomer having a cyano group, the same monomers as those used for forming the cyano group-containing unit mentioned in the aspect of 1-1) are used. Can be used.
From the viewpoint of preventing gelation during polymerization, a polymer having a cyano group is synthesized in advance, and then the polymer and a compound having a polymerizable group (hereinafter, referred to as “reactive compound” as appropriate) are reacted. And a method of introducing a polymerizable group is preferably used.

In addition, it is preferable that the polymer which has a cyano group has a reactive group as shown below for reaction with a reactive compound.
Moreover, it is preferable that the polymer having a cyano group and the reactive compound are appropriately selected so as to be a combination of the following functional groups.
Specific combinations include (polymer reactive group, functional group of reactive compound) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, Benzyl halide), (hydroxyl group, carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, halogenated benzyl) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group), etc. be able to.

Here, specifically, the following compounds can be used as the reactive compound.
That is, allyl alcohol, 4-hydroxybutane vinyl ether, 2-hydroxyethane vinyl ether, 3-hydroxypropane vinyl ether, hydroxytriethylene glycol vinyl ether, 1st terpionol, 2-methyl-2-propenol, 3-methyl-3-butenol, 3 -Methylene-2-hydroxy-norbornane, p- (chloromethyl) styrene.

2-2) Aspect in which both are radical polymerizations In a mode in which both are radical polymerizations, the synthesis method includes i) a method of copolymerizing a monomer having a cyano group and a monomer having a polymerizable group, ii) a cyano group A method of copolymerizing a monomer having a monomer and a monomer having a double bond precursor and then introducing a double bond by treatment with a base or the like; iii) reacting a polymer having a cyano group with a monomer having a polymerizable group And introducing a double bond (introducing a polymerizable group). From the viewpoint of synthesis suitability, ii) a method in which a monomer having a cyano group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like, iii) cyano In this method, a polymer having a group and a monomer having a polymerizable group are reacted to introduce a polymerizable group.

  Examples of the monomer having a polymerizable group used in the synthesis method i) include allyl (meth) acrylate and the following compounds.

  Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula (a).

In the above formula (a), A is an organic group having a polymerizable group, R ^{1 to} R ³ are each independently a hydrogen atom or a monovalent organic group, and B and C are removed by elimination reaction. This is a leaving group, and the elimination reaction referred to here is one in which C is extracted by the action of a base and B is eliminated. B is preferably eliminated as an anion and C as a cation.
Specific examples of the compound represented by the formula (a) include the following compounds.

  Further, in the synthesis method of ii), in order to convert the double bond precursor into a double bond, as shown below, a method for removing the leaving groups represented by B and C by elimination reaction, That is, a reaction in which C is extracted by the action of a base and B is eliminated is used.

  Preferred examples of the base used in the elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds. Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, Examples include potassium hydrogen carbonate and sodium hydrogen carbonate. Preferable examples of the organic amine compound include trimethylamine, triethylamine, diethylmethylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N- Methyldicyclohexylamine, N-ethyldicyclohexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, 1,4-dimethyl Piperazine, quinuclidine, 1,4-diazabicyclo [2,2,2] -octane, hexamethylenetetramine, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, Cytidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N, N'-dicyclohexylcarbodiimide (DCC), diisopropylethylamine, Schiff base, and the like. Preferable examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases may be used alone or in combination of two or more.

  Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate , Ethyl lactate, water and the like. These solvents may be used alone or in combination of two or more.

  The amount of the base used may be equal to or less than the equivalent to the amount of the specific functional group (the leaving group represented by B or C) in the compound, or may be equal to or more than the equivalent. Moreover, when an excess base is used, it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.

In the synthesis method of iii), the monomer having a polymerizable group to be reacted with a polymer having a cyano group varies depending on the type of the reactive group in the polymer having a cyano group, but has the following combinations of functional groups: Can be used.
That is, (reactive group of polymer, functional group of monomer) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, benzyl halide), (hydroxyl group) , Carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, halogenated benzyl) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group) and the like.
Specifically, the following monomers can be used.

The ratio of the polymerizable group-containing unit and the cyano group-containing unit of the cyano group-containing polymerizable polymer synthesized in the present invention as described above is preferably in the following range with respect to the entire copolymerization component.
That is, it is preferable that a polymeric group containing unit is contained with 5-50 mol% with respect to the whole copolymerization component, More preferably, it is 5-40 mol%. If it is 5 mol% or less, the reactivity (curability and polymerizability) is lowered, and if it is 50 mol% or more, it is easily gelled during synthesis and is difficult to synthesize.
Moreover, it is preferable that a cyano group containing unit is contained by 1-95 mol% with respect to the whole copolymerization component, More preferably, it is 10-95 mol%.

In addition, the cyano group-containing polymerizable polymer in the present invention may contain other units in addition to the cyano group-containing unit and the polymerizable group-containing unit. As the monomer used for forming the other unit, any monomer can be used as long as it does not impair the effects of the present invention.
However, when the polymerizable group is introduced by reacting with the polymer as described above, a small amount of reactive portion remains when it is difficult to introduce 100%, so this becomes the third unit. There is a possibility.
Specifically, when the polymer main chain is formed by radical polymerization, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Unsubstituted (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, Halogen-substituted (meth) acrylic esters such as 2-chloroethyl (meth) acrylate, ammonium group-substituted (meth) acrylic esters such as 2- (meth) acryloyloxyethyltrimethylammonium chloride, butyl (meth) acrylamide, Iso (Meth) acrylamides such as propyl (meth) acrylamide, octyl (meth) acrylamide, dimethyl (meth) acrylamide, styrenes such as styrene, vinylbenzoic acid, p-vinylbenzylammonium chloride, N-vinylcarbazole, vinyl acetate, Vinyl compounds such as N-vinylacetamide and N-vinylcaprolactam, and dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-ethylthio-ethyl (meth) acrylate, (meth) acrylic acid, 2 -Hydroxyethyl (meth) acrylate etc. can be used.
Moreover, the macromonomer obtained using the monomer of the said description can also be used.

  When the polymer main chain is formed by cationic polymerization, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol vinyl ether, di (ethylene glycol) vinyl ether, 1,4-butanediol vinyl ether, 2-chloroethyl vinyl ether, 2 -Vinyl ethers such as ethylhexyl vinyl ether, vinyl acetate, 2-vinyloxytetrahydropyran, vinyl benzoate, vinyl butyrate, styrenes such as styrene, p-chlorostyrene, p-methoxystyrene, allyl alcohol, 4-hydroxy-1- Terminal ethylenes such as butene can be used.

  The molecular weight (Mw) of the cyano group-containing polymerizable polymer in the present invention is preferably 3000 to 200,000, more preferably 4000 to 100,000.

Specific examples of the cyano group-containing polymerizable polymer in the invention are shown below, but are not limited thereto.
In addition, as for the weight average molecular weight of these specific examples, all are the range of 3000-100000.

Here, for example, in the compound 2-2-11 in the specific example, acrylic acid and 2-cyanoethyl acrylate are dissolved in, for example, N-methylpyrrolidone, and the polymerization initiator is, for example, azoisobutyronitrile (AIBN). ) And then glycidyl methacrylate can be synthesized by addition reaction using a catalyst such as benzyltriethylammonium chloride and a polymerization inhibitor such as tertiary butylhydroquinone. .
Further, for example, in the compound 2-2-19 in the above specific example, the following monomers and p-cyanobenzyl acrylate are dissolved in a solvent such as N, N-dimethylacrylamide, and polymerization is initiated such as dimethyl azoisobutyrate. It can be synthesized by performing radical polymerization using an agent and then dehydrochlorinating using a base such as triethylamine.

  In the present invention, as a compound having a polymerizable group and an interactive group, the formation density of the graft polymer is improved by using a macromer or a polymer having a plurality of polymerizable groups in the side chain as well as the terminal, A uniform and high density graft polymer layer is formed, which is preferable. In this case, even when the electroless plating catalyst or its precursor is applied, the adhesion density is improved and an excellent plating receptive region can be obtained. When a macromer or a polymer is used as the polymerizable compound, since a polymerizable group exists at a high density, if a polymerization initiator is allowed to coexist or is grafted using a known method using a high energy electron beam, The generation of homopolymer is remarkable, and the removability of the formed homopolymer is further lowered. Therefore, it can be understood that the effect of the present invention is remarkable when such a polymerizable compound is used.

  From the viewpoint of the production method, when a polymerizable compound is brought into contact with the substrate surface by a coating method using a polymer, a polymer coating film having a uniform thickness is easily formed, which is necessary for monomer coating. This eliminates the need for a cover for protecting the coating liquid and makes it possible to uniformly contact the polymerizable compound at an arbitrary thickness, so that the uniformity of the formed graft polymer is improved and the production suitability is also improved. Is. For these reasons, in the production of a large area or a large amount, it is particularly useful in terms of production suitability to use a polymer having an interactive group and a polymerizable group.

If the solvent used in the composition containing a compound having such a polymerizable group and an interactive group is soluble in a compound having a polymerizable group and an interactive group, which are main components, a hydrophilic monomer, etc. Although there is no restriction | limiting in particular, Aqueous solvents, such as water and a water-soluble solvent, are preferable, and you may add surfactant further to these mixtures and a solvent.
Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone and cyclohexanone, amides such as formamide and dimethylacetamide. System solvents, and the like.
Among these, when a composition using a cyano group-containing polymerizable polymer is used, amide, ketone, and nitrile solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propio Nitrile and N-methylpyrrolidone are preferred.
Moreover, when apply | coating the composition containing a cyano group containing polymeric polymer, the solvent whose boiling point is 50-150 degreeC is preferable from handling ease. In addition, these solvents may be used alone or in combination.

  The surfactant that can be added to the solvent as needed may be any that dissolves in the solvent. Examples of such surfactants include an anionic surfactant such as sodium n-dodecylbenzenesulfonate. Agents, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate (commercially available) Examples of the product include a trade name “Tween 20” and the like, and nonionic surfactants such as polyoxyethylene lauryl ether.

  Moreover, a plasticizer can also be added as needed. Usable plasticizers include general plasticizers such as phthalates (dimethyl ester, diethyl ester, dibutyl ester, di-2-ethylhexyl ester, dinormal octyl ester, diisononyl ester, dinonyl ester, diisodecyl ester). Ester, butyl benzyl ester), adipic acid ester (dioctyl ester, diisononyl ester), azelain san dioctyl, sebacin sun ester (dibutyl ester, dioctyl ester) tricresyl phosphate, acetyl citrate tributyl, epoxidized soybean oil, trimellit High boiling solvents such as trioctyl acid, chlorinated paraffin, dimethylacetamide, and N-methylpyrrolidone can also be used.

When the graft polymer is produced by bringing the composition into contact with the substrate surface in a liquid state, it can be arbitrarily performed, but the coating amount when applying the composition to the substrate surface in the coating method is sufficient. from the viewpoint of obtaining a Do coating film is preferably 0.1 to 10 g / m ² in terms of solid content, especially 0.5 to 5 g / m ² preferably.

-Energy provision-
As an energy application method for generating an active site at a polymerization initiation site present on the substrate surface, for example, radiation irradiation such as heating or exposure can be used. For example, light irradiation with a UV lamp, visible light, or the like, heating with a hot plate, or the like is possible.
Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Moreover, g line | wire, i line | wire, Deep-UV light can also be used.

  In the case of applying energy by exposure, it is preferable to use scattered light as irradiation light from the viewpoint of bonding the graft polymer to the entire recess or through-hole formed in the substrate. As an exposure apparatus that can be used for exposure by scattered light, for example, an optical surface treatment experimental apparatus manufactured by Mario Network, Inc .: OPL-16 (ultraviolet wavelength: 254 nm), 254 nm UV light cleaning manufactured by MBK Microtech Co., Ltd. Apparatus, etc.

  The time required for applying energy is usually between 10 seconds and 5 hours, although it varies depending on the amount of the graft polymer produced and the light source.

As described above, the polymer layer in the present invention is formed.
The formation of the polymer layer can be confirmed, for example, by applying a 0.1% methylene blue aqueous solution on the substrate after forming the polymer layer and observing that the polymer layer forming portion is colored blue.

<(C) The process of providing an electroless plating catalyst or its precursor on a polymer layer>
In this step, an electroless plating catalyst or a precursor thereof is applied on the polymer layer formed in the step (B).

-Electroless plating catalyst-
The electroless plating catalyst used in this step is mainly a zero-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable because of their good handleability and high catalytic ability. As a method for fixing the zero-valent metal to the interactive region, for example, a metal colloid whose charge is adjusted so as to interact with an interactive group on the interactive region is applied to the interactive region. A technique is used. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here, and by interacting the metal colloid whose charge is adjusted in this way with the interactive group of the graft pattern, A metal colloid (electroless plating catalyst) can be selectively adsorbed to the graft polymer.

-Electroless plating catalyst precursor-
The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion, which is an electroless plating catalyst precursor, may be used as an electroless plating catalyst after being applied to the polymer layer and before being immersed in the electroless plating bath by changing it to a zero-valent metal by a reduction reaction. The electroplating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

Actually, the metal ion which is an electroless plating precursor is applied on the graft pattern in the form of a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) n, MCn, M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.

  As a method for applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor onto a graft pattern, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is added with an appropriate solvent. A solution containing dissolved and dissociated metal ions is prepared, and the solution is applied to the surface of the substrate on which the graft pattern exists, or the substrate having the graft pattern is immersed in the solution. Contacting a solution containing a metal ion to adsorb a metal ion to an interactive group on the interactive region by using an ion-ion interaction or a dipole-ion interaction; or The interaction region can be impregnated with metal ions. From the viewpoint of sufficiently performing such adsorption or impregnation, the metal ion concentration or the metal salt concentration in the solution to be contacted is preferably in the range of 0.01 to 50% by mass, preferably 0.1 to 30%. More preferably, it is in the range of mass%. Further, the contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour.

<(D) Process of forming a metal layer by electroless plating>
In this step, the metal layer is formed by performing electroless plating. That is, by performing electroless plating in this step, a high-density metal layer is formed inside or on the polymer layer formed in the step (B). The metal layer formed in this step has excellent conductivity and adhesion.

  Further, when the step (D ′) described later is performed, the metal layer (electroless plating layer) formed in this step functions as a seed layer in electrolytic plating. Furthermore, the metal layer formed in this step is used as a barrier layer for preventing migration in the metal layer (electrolytic plating layer) formed in the step (D ′) by selecting the type of metal to be deposited. It can also function.

-Electroless plating-
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved. The conductivity can be increased by depositing a metal.
The electroless plating in this step is performed, for example, by washing the substrate provided with the electroless plating catalyst obtained in the step (C) with water to remove excess electroless plating catalyst (metal), and then electrolessly plating. Immerse in a plating bath. As the electroless plating bath to be used, a generally known electroless plating bath can be used.
In addition, when the substrate to which the electroless plating catalyst precursor is applied in a pattern is immersed in the electroless plating bath with the electroless plating catalyst precursor adsorbed or impregnated in the craft pattern, the substrate is washed with water. After removing an excess precursor (metal salt etc.), it is immersed in an electroless plating bath. In this case, reduction of the precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a generally known electroless plating bath can be used as described above.

The composition of a general electroless plating bath is as follows: 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
Copper, tin, lead, nickel, gold, palladium, rhodium, etc. are known as the types of metals used in the electroless plating bath, and copper and gold are particularly preferable from the viewpoint of conductivity.

  As the metal used in the electroless plating bath, a metal having autocatalytic properties may be used from the viewpoint of plating application efficiency. Examples of the self-catalytic metal include nickel, cobalt, iron, copper, silver, gold, rhodium, palladium, platinum, iridium, molybdenum, ruthenium, tin, tungsten, and zinc. Among these, nickel, palladium, molybdenum, and tungsten are more preferable as the self-catalytic metal.

In addition, there are optimum reducing agents and additives according to the above metals. For example, a copper electroless plating bath contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate and sodium succinate as complexing agents. It is included. In addition, the palladium electroless plating bath contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

  The film thickness of the metal layer thus formed can be controlled by the concentration of the metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, etc. Is preferably 0.5 μm or more, more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

  When the metal film formed in this step functions as a barrier layer for the metal film (eg, Cu film) formed in the step (D ′), the type of metal used in the electroless plating bath As nickel, cobalt, or chromium is preferable. As the composition and plating conditions of the electroless plating bath that can be applied in this case, for example, the conditions of paragraph numbers [0022] to [0024] of JP-A No. 2003-328184 can be applied. By making the metal of the electroless plating bath nickel, cobalt, or chromium, the ability to suppress migration can be further obtained.

  In the metal layer obtained as described above, fine particles of the electroless plating catalyst and the plating metal are firmly dispersed in the surface graft film by cross-sectional observation by SEM, and further relatively large particles are deposited thereon. It is confirmed that Since the interface is in a hybrid state of the graft polymer and the fine particles, the adhesion is good even if the unevenness of the interface between the substrate (organic component) and the inorganic substance (electroless plating catalyst or plating metal) is 500 nm or less.

<(D ′) Step of Electroplating Using Metal Layer as Seed Layer>
In the method for manufacturing a wiring board according to the present invention, it is preferable that after the electroless plating in the step (D), the formed metal layer is used as a seed layer and further electrolytic plating is performed. As a result, a metal layer (electrolytic plating layer) having an arbitrary thickness can be easily formed on the metal layer having excellent adhesion to the substrate. The electrolytic plating layer formed by the step (D ′) may be an alloy layer containing a plurality of metals.

  As a method of electrolytic plating, a conventionally known method can be used. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned, and copper, gold, and silver are preferable from the viewpoint of conductivity, and copper is used. More preferred.

  The film thickness of the metal layer formed by electrolytic plating varies depending on the application, and can be controlled by adjusting the metal concentration, immersion time, or current density contained in the plating bath. . In addition, the film thickness in the case of using it for general electric wiring etc. is preferably 0.5 μm or more, and more preferably 3 μm or more from the viewpoint of conductivity.

  Further, between the formation of the electroless plating layer by the step (D) and the formation of the electroplating layer by the step (D ′), the electrolytic plating layer formed by the step (D ′) is different. It can also have the process of providing another metal layer. Specifically, for example, after the step (D) and before the step (D ′), a metal layer made of a metal different from the metal used in the step (D ′) (hereinafter referred to as “intermediate” as appropriate). (Hereinafter referred to as “metal layer”), an electrolytic plating layer formed by the step (D ′) can be provided. For example, when the electrolytic plating layer formed by the step (D ′) is made of copper, the intermediate metal layer can be formed of chromium, lead, nickel, gold, silver, tin, zinc, or the like other than copper. .

  Further, the intermediate metal layer may be formed by an eutectoid alloy plating bath. Alloy plating baths that can be applied in this case include plated silver-tin, silver-palladium, silver-bismuth, silver-antimony, silver-thallium, silver-rhodium, cobalt-nickel, cobalt-tungsten, cobalt-chromium, cobalt -Molybdenum, cobalt-palladium, cobalt-tin, cobalt-phosphorus, cobalt-zinc, cobalt-thallium, cobalt-boron, tungsten-nickel, tungsten-molybdenum, tin-silver, tin-cobalt, tin-nickel, tin-bismuth , Tin-manganese, tin-indium, nickel-zinc, nickel-phosphorus, nickel-platinum, nickel-rhodium, nickel-tin, nickel-thallium and the like. As the composition of the alloy plating bath, the composition of the electrolytic plating bath described in [0035] to [0038] of JP-A No. 2003-328184 can be applied. By providing such an intermediate metal layer, the ability to suppress migration can be further enhanced.

-Drying process-
In the manufacturing method of this invention, it is preferable from a viewpoint of the adhesive improvement of a board | substrate and wiring to perform a drying process further after the said (D) process or (D ') process.
The drying process in the drying step may be any means, and specifically can be performed by means such as natural drying, heat drying, reduced pressure drying, reduced pressure heat drying, and air blowing. Among these, from the viewpoint of suppressing the deterioration of the polymer layer due to drying, it is preferable to perform the drying treatment at room temperature or a temperature condition in the vicinity thereof. Specifically, each drying process of natural drying at normal temperature, reduced-pressure drying under normal temperature conditions, and normal temperature ventilation drying is preferable.

  From the viewpoint of removing moisture as much as possible without heating, it is preferable to carry out these drying treatments for 1 hour or more, more preferably 24 hours or more. The drying treatment conditions may be appropriately selected in consideration of required adhesion and the like. Specifically, the substrate after the step (D) or (D ′) is, for example, about 25 ° C. A method of storing and drying in a temperature atmosphere for about 1 to 3 days, about 1 to 3 weeks, or about 1 to 2 months, about 1 to 3 days under reduced pressure by a normal vacuum dryer, or 1 to 3 Examples include a method of storing and drying for about a week.

  Although the effect of improving the adhesion between the substrate and the wiring by performing such a drying process is not clear, the moisture that reduces the adhesion by performing the sufficient drying causes the water content in the metal part and the polymer layer. It is presumed that it is possible to suppress a decrease in adhesion due to moisture by preventing it from being held at the interface. In order to prevent oxidation of the surface of the metal film made of copper or the like during drying, it is preferable to apply an antioxidant to the surface of the metal film before the drying step. As the antioxidant, those commonly used can be applied, and for example, amidimide benzene and the like can be used.

<(E) Step of removing unnecessary metal layer on the substrate and wiring so that the metal layer remains only in the recess or the through hole>
In this step, wiring is performed by removing an unnecessary metal layer on the substrate so that the metal layer remains only in the recess or the through hole with respect to the substrate after the step (D) or (D ′). Form.

  As a method for removing an unnecessary metal layer in this step, a polishing process such as CMP or an etching process can be used. For example, the polishing treatment described in JP-A-2002-348697, JP-A-2006-147701, JP-A-2004-363283, JP-A-2003-283127, JP-A-2003-60350, etc., JP-A-2006 The etching treatment described in each publication such as JP-A-147701 and JP-A No. 2004-95983 can be applied to this step.

  When a multilayer wiring board is formed by laminating a plurality of wiring boards obtained by the present invention, the surface of the formed wiring may be roughened by a process such as a roughening process using potassium permanganate. Good. By roughening the surface of the wiring, the adhesion between the wiring boards can be improved.

  Hereinafter, the embodiment of the method for manufacturing a wiring board according to the present invention will be described more specifically.

<Embodiment 1>
An example of an embodiment of a method for manufacturing a wiring board according to the present invention will be described.
In the first embodiment, the formation of the concave portion or the through hole in the step (A) is performed according to the “formation mode (1)”, and then the steps (B) to (E) are performed.

FIG. 2 is a flowchart showing an outline of a manufacturing process example of a wiring board in the manufacturing method of the present invention.
FIG. 2A shows a convex portion in the molding material 20 using a molding material 20 having a surface provided with convex portions 22a and 22b for forming concave portions and through holes in the substrate in the step (A) in the present invention. A state in which the surface provided with 22a and 12b and the resin substrate 24 are overlapped and pressurized is shown.

  The resin substrate 24 is made of a thermoplastic resin. Before pressurizing the molding material 20 to the resin substrate 24, the resin substrate 24 is heated and softened, whereby the concave portions are formed by the convex portions 22 a of the molding material 20, the through holes are formed by the convex portions 22 b, and the resin substrate 24. Each can be easily formed (step (A)). .

  (A) A polymer layer is formed on the resin substrate 24 after completion of the step (step (B)), and then electroless plating or a precursor thereof is applied to the polymer layer (step (C)). By performing electroless plating (step (D)), the metal layer 26 is formed.

  FIG. 2B shows the resin substrate 24 on which the metal layer 26 is formed. As shown in FIG. 2B, the metal layer 26 including the recesses 28 and the insides of the through holes 30 is formed on the surface serving as the wiring formation region in the resin substrate 24.

  The resin substrate 24 on which the metal film 26 is formed is subjected to electrolytic plating using this as a plating seed layer (step D ′). As a result, as shown in FIG. 2C, the plating metal 32 that becomes the wiring is deposited on the surface of the resin substrate 24.

  The metal layer 26 may be configured to function as a barrier layer. As an example in this case, the aspect which forms the thin nickel plating layer as the metal layer 26 is mentioned.

  As shown in FIG. 2C, the electrolytic plating is performed until the recesses 28 and the through holes 30 formed in the resin substrate 24 are filled with the plating metal 32. In this embodiment, electrolytic copper plating is applied as electrolytic plating.

  Here, for the polymer layer, electroless plating, electrolytic plating, and the like formed in this embodiment, for example, the contents described in Example 1 of JP-A-2006-19675 are similarly applied to this embodiment. Can be applied.

After the electrolytic plating is performed so that the concave portion 28 and the through hole 30 are filled with the plating metal 30, the surface of the resin substrate 20 on the side where the plating metal 30 is deposited is polished by a CMP method or the like (step (E)).
As shown in FIG. 2D, this polishing operation removes unnecessary plating metal 32 deposited on the surface other than the recesses 28 and the through holes 30 formed in the resin substrate 24, thereby removing the recesses 28 and the through holes. The plated metal 32 is left only in the holes 30.
Since the convex portions 22a and 22b provided on the molding material 20 are formed in advance according to the wiring pattern shape, the concave portion 28 and the through hole 30 are formed on the resin substrate 24 in the same pattern as the convex portions 22a and 22b. As a result, a patterned wiring 34 is formed on the resin substrate 24.
As described above, the wiring board 36 of the present invention is obtained.

  As mentioned above, although the manufacturing method of the wiring board 36 by this invention was demonstrated by Embodiment 1, this invention is not limited to this embodiment.

  For example, in Embodiment 1 described above, the concave portions 28 and the through holes 30 are formed by pressing the convex portions 22a and 22b formed on the molding material 20 against the resin substrate 24. Conventional lithography and etching techniques can be used. Further, a laser can be used for forming the recess. Further, conventional etching can be applied to the surface treatment after electrolytic plating instead of the CMP method. When applying etching, it is preferable to perform etching with a ferric chloride aqueous solution.

[Embodiment 2]
Another example of the embodiment of the method for manufacturing a wiring board of the present invention will be described.
In the second embodiment, the formation of the recess or the through hole in the step (A) is performed by the “formation mode (5)”, and then each step of the steps (B) to (E) is performed.

<(A) Process>
After immersing the entire surface of a polyimide resin substrate (Kapton 200H, manufactured by Toray DuPont Co., Ltd.) in a 30% by volume hydrazine monohydrate aqueous solution at 25 ° C. for 3 minutes, “OPC” manufactured by Okuno Pharmaceutical Co., Ltd. The catalyst is applied for 7 minutes at 20 ° C. using “−80 Catalyst M”. The polyimide resin substrate after the application of the catalyst is washed with water and subjected to an accelerating treatment at 20 ° C. for 10 minutes using “OPC-555 accelerator” manufactured by Okuno Pharmaceutical Co., Ltd.
Thereafter, electroless copper plating is performed on the entire surface of the polyimide resin substrate under the following conditions.

-Composition of electroless copper plating solution-
_{CuSO 4 · 5H 2 O 10g /} L
EDTA · 2Na 25g / L
37% HCHO 5mL / L

-Electroless copper plating conditions-
Temperature: 65 ° C
Time: 10 minutes Stirring: Stirring with air pH: 12.5 (adjusted with NaOH)

  Thereafter, electrolytic copper plating is performed on the copper surface of the obtained substrate under the following conditions to form a 1 μm thick copper coating (copper layer A) on the entire surface of the polyimide resin substrate.

-Composition of electrolytic copper plating solution-
_{CuSO 4 · 5H 2 O 80g /} L
H ₂ SO ₄ 180 g / L

-Electrolytic copper plating conditions-
Cathode current density: 3 A / dm ²
Temperature: 25 ° C
Stirring: Air and cathode rocker Time: 2 minutes

  Thereafter, a negative photoresist “PMER HC-600” manufactured by Tokyo Ohka Kogyo Co., Ltd. was applied to the surface of the copper layer A where the metal mask was formed to a thickness of 45 μm. After uniformly coating, it is dried at 60 ° C. for 30 minutes.

Thereafter, a negative mask on which the metal mask having a width of 40 μm and an interval of 40 μm is formed on the surface of the “PMER HC-600” layer on the metal mask forming surface, and also on the surface of the “PMER HC-600” layer on the polyimide resin aperture surface. Set a negative mask on which 100 via holes having an outer diameter of 120 μm are formed, and irradiate each resist layer with ultraviolet rays of 700 mJ / cm ² and 30 mJ / cm ² .

  Next, the “PMER HC-600” layer on the metal mask forming surface was developed, and the exposed copper layer A surface was subjected to electrolytic copper plating under the following conditions to form a metal mask.

-Composition of electrolytic copper plating solution-
_{CuSO 4 · 5H 2 O: 80g} / l
H ₂ SO ₄ : 180 g / l

-Plating conditions-
Cathode current density: 3 A / dm ²
Temperature: 25 ° C
Stirring: Air and cathode rocker Time: 1 hour

  Then, after developing the “PMER HC-600” layer on the polyimide aperture surface and peeling off the “PMER HC-600” layer on the metal mask forming surface, the exposed copper layer A was converted to 45 g / L ammonium persulfate and 50 mL / L sulfuric acid. The aqueous solution containing L was dissolved and removed, and then “PMER HC-600” on the polyimide pore surface was peeled off.

By the above processing, a 1 μm thick copper layer A is patterned on the polyimide aperture surface as an etching resist (metal mask) for the polyimide resin substrate.
Thereafter, the exposed polyimide resin portion of the polyimide resin substrate is etched with hydrazine monohydrate at 50 ° C. for 4 minutes to form wiring grooves (recesses in the present invention) and via hole portions (through holes in the present invention).

  The metal mask patterned as an etching resist is plated in the groove, and after filling the groove, the metal mask is removed together with an unnecessary upper portion of the wiring by CMP.

<Process (B) to (E)>
(A) Steps (B) to (E) are performed on the polyimide substrate after the end of the steps in the same manner as in the first embodiment.
As described above, the wiring board of the present invention is obtained according to the second embodiment.

[Manufacturing method of multilayer wiring board and multilayer wiring board obtained thereby]
One aspect of the method for manufacturing a multilayer wiring board of the present invention is that two or more wiring boards (wiring boards of the present invention) obtained by the method for manufacturing a wiring board of the present invention are laminated via an adhesive layer. Features. Hereinafter, this aspect is appropriately referred to as “multilayer wiring board manufacturing method (1)”.

  In the manufacturing method (1) of the multilayer wiring board, as an adhesive layer applied to the bonding between the wiring boards, an epoxy adhesive, ABF-GX13 (manufactured by Ajinomoto Co., Inc.), Hitachi Chemical Co., Ltd. “MCL series”, “R-05A0, R-5610” of Matsushita Electric Works, Ltd., “38N, 49N” of Aaron, etc., “SAY, EP-188” of Arisawa Manufacturing Co., Ltd., Sumitomo Bakelite ( A prepreg such as “EI-6788”, etc., can be used.

  In another aspect of the method for manufacturing a multilayer wiring board of the present invention, (a) a first insulator layer is formed on a wiring formation surface of the wiring board of the present invention, and a wiring formation region is formed on the first insulator layer. And (b) a polymer layer comprising a polymer having a functional group that interacts with the electroless plating catalyst or a precursor thereof and directly binding to the substrate surface. (C) a step of providing an electroless plating catalyst or a precursor thereof on the polymer layer, (d) a step of forming a metal layer by performing electroless plating, and (e) the recess. Or a step of forming a wiring by removing an unnecessary metal layer existing on the insulator layer so that the metal layer remains only in the through hole. Hereinafter, this aspect is appropriately referred to as “multilayer wiring board manufacturing method (2)”.

<(A) Process>
In the step (a), a first insulator layer is formed on the wiring formation surface of the wiring board of the present invention, and a recess or a through-hole serving as a wiring formation region is formed in the first insulator layer.

  (A) As a 1st insulator layer formed at a process, resin, such as a polyimide resin and an epoxy resin, can be used.

  The formation of the recess or the through hole in the step (a) can be performed in the same manner as the formation of the recess or the through hole described in detail in the step (A) in the method for manufacturing a wiring board of the present invention described above.

<(B) Process to (e) Process>
Steps (b) to (e) are steps similar to steps (B) to (E) in the above-described method for manufacturing a wiring board of the present invention, and are described in detail with respect to steps (B) to (E). The same applies to the steps (b) to (e).

In the multilayer wiring board manufacturing method (2), (a ′) a second insulating layer is formed on the wiring forming surface after the end of the step (e), and a wiring forming region is formed on the second insulating layer. After performing the process of forming the recessed part or through-hole which becomes, you may perform the said (b) process-(e) process further.
The formation of the second insulator layer in the step (a ′) can be performed in the same manner as the formation of the first insulator layer in the step (a).
Further, the steps (a ′) and (b) to (e) may be repeated a plurality of times, whereby a multilayer wiring board in which build-up layers are laminated in multiple stages can be obtained.

  Further, the step (D ′), the drying step, the step of forming a barrier layer, and the like can be performed in the same manner in the multilayer wiring board manufacturing method (2).

  The multilayer wiring board of the present invention is obtained by the manufacturing method (1) and (2) of the multilayer wiring board of the present invention, has wiring having high adhesion to the substrate, and has excellent high frequency characteristics. It is a multilayer wiring board

It is a figure which shows an example of the molding material used for this invention. It is a flowchart which shows the outline of the manufacturing process example of the wiring board in this invention.

Explanation of symbols

10, 20 Molding material 12, 22 Convex part 24 Resin substrate 26 Metal layer 28 Concave part 30 Through-hole 32 Plating metal 34 Wiring 36 Wiring board

Claims (22)

(A) a step of forming a recess or a through-hole to be a wiring formation region on one surface or both surfaces of the substrate;
(B) forming a polymer layer made of a polymer having a functional group that interacts with an electroless plating catalyst or a precursor thereof and directly binding to the substrate surface on the substrate;
(C) providing the electroless plating catalyst or a precursor thereof on the polymer layer;
(D) forming a metal layer by performing electroless plating;
(E) forming a wiring by removing an unnecessary metal layer present on the substrate so that the metal layer remains only in the recess or the through hole;
A method of manufacturing a wiring board, comprising:   2. The method of manufacturing a wiring board according to claim 1, further comprising: (D ′) a step of performing electrolytic plating using the metal layer as a seed layer to form an electrolytic plating layer after the step (D). 3.   The step (A) uses a molding material having a surface provided with a convex portion for forming the concave portion or the through hole, and pressurizes the surface of the molding material provided with the convex portion and the substrate. The method for manufacturing a wiring board according to claim 1, wherein the through hole or the recess is transferred and formed on the substrate.   The method for manufacturing a wiring board according to claim 1, wherein the step (A) is a step of forming the concave portion or the through hole in the substrate by laser light irradiation.   The method for manufacturing a wiring board according to claim 1, wherein the step (A) is a step of forming the concave portion or the through hole in the substrate by etching using a photoresist.   The method for manufacturing a wiring board according to claim 1, wherein the step (A) is a step of forming the concave portion or the through hole in the substrate by embossing.   The method for manufacturing a wiring board according to claim 1, wherein the step (A) is a step of forming the concave portion or the through hole in the substrate by etching using a metal mask.   The method for manufacturing a wiring board according to claim 1, wherein the removal of the plated metal in the step (E) is performed by a polishing process.   The method for manufacturing a wiring board according to claim 1, wherein the removal of the plating metal in the step (E) is performed by etching.   The method for manufacturing a wiring board according to claim 1, wherein a drying step is performed after the step (D) or the step (D ′).   The method for manufacturing a wiring board according to claim 1, wherein the metal layer formed by the step (D) is a metal layer containing nickel, palladium, molybdenum, or tungsten.   12. The wiring according to claim 1, wherein the electroplating layer formed by the step (D ′) is an electroplating layer containing nickel, cobalt, or chromium. A method for manufacturing a substrate.   The method for manufacturing a wiring board according to any one of claims 1 to 12, wherein the substrate has a surface irregularity of 500 nm or less.   The method for manufacturing a wiring board according to any one of claims 1 to 12, wherein the substrate has a surface irregularity of 100 nm or less.   The method for manufacturing a wiring board according to claim 1, wherein adhesion between the substrate and the metal layer is 0.2 kN / m or more.   The method for manufacturing a wiring board according to any one of claims 1 to 15, wherein the substrate is a substrate made of an insulating resin having a dielectric loss tangent at 1 GHz of 0.01 or less.   The method for manufacturing a wiring board according to any one of claims 1 to 15, wherein the substrate is a substrate made of an insulating resin having a dielectric constant of 3.5 or less at 1 GHz.   A wiring board obtained by the method for manufacturing a wiring board according to any one of claims 1 to 17.   A multilayer wiring board comprising two or more of the wiring boards according to claim 18 laminated through an adhesive layer. (A) forming a first insulator layer on the wiring formation surface of the wiring board according to claim 18 and forming a recess or a through-hole serving as a wiring formation region in the first insulator layer;
(B) forming on the insulator layer a polymer layer made of a polymer having a functional group that interacts with the electroless plating catalyst or a precursor thereof and directly bonding to the substrate surface;
(C) providing an electroless plating catalyst or a precursor thereof on the polymer layer;
(D) performing electroless plating to form a metal layer;
(E) forming a wiring by removing an unnecessary metal layer present on the insulator layer so that the metal layer remains only in the recess or the through hole;
A method for producing a multilayer wiring board, comprising:   (A ′) A step of forming a second insulator layer on the wiring formation surface after the completion of the step (e) and forming a recess or a through hole serving as a wiring formation region in the second insulator layer. 21. The method of manufacturing a multilayer wiring board according to claim 20, further comprising performing the steps (b) to (e).   A multilayer wiring board obtained by the method for manufacturing a multilayer wiring board according to any one of claims 20 and 21.

Images