JP2007134396A - Laminated body for printed wiring board, multilayer metal wiring pattern forming method using the same, and metal thin film - Google Patents

Abstract

A metal wiring having high-definition wiring and multi-layer wiring, which can easily form a conductive layer having excellent adhesion to an insulating film and small irregularities at the interface with the insulating film on any solid surface. Patterns can be provided. Moreover, by using the laminate for a printed wiring board of the present invention, a method for forming a laminate for a printed wiring board useful as an interposer between multilayer wirings having a high-definition metal wiring pattern can be provided.
A photosensitive resin component layer on a support, an insulating resin composition layer capable of generating reactive active species upon application of energy, and a polymer compound that reacts with the insulating resin composition layer And a reactive polymer precursor layer containing a compound capable of forming a printed wiring board.
[Selection figure] None

Description

  The present invention relates to a laminate that can be suitably used for producing a multilayer printed wiring board, and a multilayer metal wiring pattern forming method using the same, and more specifically, a multilayer printed wiring board having high-density wiring used in the field of electronic materials. The present invention relates to a laminate for a printed wiring board that can be easily manufactured, and a multilayer metal wiring pattern forming method that supports high density mounting using the same.

In recent years, along with demands for higher functionality of electronic devices, electronic components have been densely integrated, and further, high-density mounting has been progressing. Is becoming more and more dense. 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. However, when the build-up multilayer wiring board is subjected to thermocompression bonding for the lamination between the multilayers, there is a concern that the connection strength between the layers connected by the fine vias may be reduced.
In forming the fine wiring, usually, a metal layer for forming the metal wiring portion is formed on the entire insulating layer, and the predetermined portion is removed by etching or the like to remove the wiring portion from the subtractive method, or An additive method or the like in which a metal wiring portion formed by plating or the like is formed directly or indirectly on an insulating layer is used.
Under such circumstances, in a multilayer wiring board, a core in which wiring layers are arranged on both sides of a core base material is assumed to be capable of accommodating a fine wiring pattern at a higher density than a conventional bonded wiring board. A build-up type multilayer wiring board (hereinafter also referred to as a build-up board) of a build-up type in which a build-up layer composed of an insulating layer and a wiring layer is further laminated in order on both surfaces of the core board. However, various types have been developed, and the production methods are various.

In recent years, along with further miniaturization and weight reduction of electronic devices, wiring boards have been reduced in weight and thickness.
However, in the conventional multilayer buildup substrate, the core substrate is usually 0.4 mm or more in thickness, and one buildup layer formed by laminating an insulating layer and a wiring layer thereon has a thickness of about 60 μm. Therefore, it has been difficult to obtain a thin wiring board of 0.5 mm or less.
On the other hand, an interposer for a package useful for forming a multilayer wiring board has been proposed (see, for example, Patent Document 1). In forming a wiring, in particular, an aluminum layer is deposited to improve adhesion to the board. There is a problem that it is necessary and the process is complicated.
Thus, in producing a high-density multilayer wiring board, not only high-definition wiring is formed on the substrate surface, but also as an interposer, the formation of via holes that connect the wirings between the multilayer wirings and their openings In addition, the formation of wiring in the above is also an important issue, and realization of these is desired.
JP-A-2005-33153

An object of the present invention, which has been made in consideration of the above-mentioned conventional technical problems, is to easily form a conductive layer on an arbitrary solid surface with excellent adhesion to an insulating film and small irregularities at the interface with the insulating film. Accordingly, an object of the present invention is to provide a metal wiring pattern having high-definition wiring and multi-layer wiring.
Another object of the present invention is to provide a method for forming a laminate for a printed wiring board useful as an interposer between multilayer wirings having a high-definition metal wiring pattern, using the laminate for a printed wiring board of the present invention. Is to provide.

As a result of intensive studies, the present inventor can solve the above problem by a laminate having an insulating resin composition layer and a polymer precursor layer capable of forming a graft polymer on the surface of the photosensitive structural material layer. The present invention has been completed.
That is, the configuration of the present invention is as follows.
<1> On the support, a photosensitive resin structural material layer, an insulating resin composition layer capable of generating reactive active species by applying energy, and a polymer compound that reacts with the insulating resin composition layer And a reactive polymer precursor layer containing a compound capable of forming a laminated body for producing a printed wiring board.
<2> The laminate for producing a printed wiring board according to <1>, wherein the photosensitive resin structural material layer is an insulating resin.
<3> The laminate for a printed wiring board according to <1> or <2>, wherein the photosensitive resin structural material layer is one or more selected from a photosensitive polyimide resin and a photosensitive epoxy resin.

<4> Using the laminate for a printed wiring board according to any one of <1> to <3>, disposing the photosensitive resin structural material layer in contact with a substrate surface having a conductive film, By exposing from the reactive polymer precursor layer side, a graft polymer is formed in the exposed region, and then the region where the via hole is to be formed is exposed and developed, and an opening is formed in the photosensitive resin structural material layer. After forming the opening, a conductive material is attached to the graft polymer to form a conductive layer in a pattern on the insulating resin composition layer, and the opening is filled with the conductive material, A method for forming a multilayer metal wiring pattern, comprising connecting a conductive layer on a substrate and a conductive layer formed on an insulating resin composition layer.
<5> The method for forming a multilayer metal wiring pattern according to <4>, wherein the opening is filled with a conductive material by metal plating.
<6> The method for forming a multilayer metal wiring pattern according to <4>, wherein the opening is filled with a conductive material by filling the opening with metal fine particles.
<7> Any one of <4> to <6>, wherein an exposure wavelength for generating the graft polymer and an exposure wavelength for forming an opening in the photosensitive resin structural material layer are different from each other 2. A method for forming a multilayer metal wiring pattern according to claim 1.
<8> The multilayer metal wiring pattern according to <7>, wherein an exposure wavelength for forming an opening in the photosensitive resin structural material layer is longer than an exposure wavelength for generating a graft polymer Forming method.
<9> The multilayer metal wiring pattern according to <7>, wherein an exposure wavelength for forming an opening in the photosensitive resin structural material layer is shorter than an exposure wavelength for generating a graft polymer Formation method <10> Any one of <1> to <9>, wherein an average roughness (Rz) measured by JIS B0601 10-point average height method on the surface of the insulating resin composition layer is 3 μm or less A metal pattern forming method formed by the method according to item 1.
<11> A metal thin film formed by the metal pattern forming method according to any one of <1> to <10>, wherein unevenness at an interface with the substrate is 100 nm or less. .
<12> A metal thin film formed by the method for forming a metal pattern according to any one of <1> to <10>, wherein the adhesion with the substrate is 0.5 kN / m or more. Metal thin film.

By using the laminate for producing a printed wiring board of the present invention, a conductive layer having excellent adhesion with an insulating film can be easily formed on a wiring formed on an arbitrary insulating film, and A high-definition wiring between the wiring and a conductive layer newly formed on the insulating film can be easily formed.
The printed wiring board laminate of the present invention is disposed on the surface of the substrate (inner circuit board) having a conductive metal wiring pattern so that the photosensitive resin structural material layer is in contact with the laminate, and exposed to light. Both high-definition wiring and circuit formation between the conductive film previously formed on the substrate surface and the wiring can be easily performed, and a final multilayer metal wiring pattern can be obtained.
In the laminate of the present invention, the insulating film is preferably an insulating film containing a polymerization initiator in an insulating resin, and the polymer precursor layer is a graft polymer bonded directly to the surface of the insulating film by applying energy. It is preferable to contain the compound which has a polymerizable double bond which can form.

According to the present invention, it is possible to easily form a conductive layer having excellent adhesion to an insulating film and small irregularities at the interface with the insulating film on an arbitrary solid surface, thereby providing high-definition wiring and multi-layer wiring. A metal wiring pattern can be provided.
Moreover, by using the laminate for a printed wiring board of the present invention, a method for forming a laminate for a printed wiring board useful as an interposer between multilayer wirings having a high-definition metal wiring pattern can be provided.
The multilayer metal wiring pattern obtained by the present invention has a fine wiring pattern with excellent high-frequency characteristics, and can easily form a high-definition circuit between multilayer wirings. It can be suitably used.

The laminate for a printed wiring board of the present invention comprises a photosensitive structural material layer that holds the laminate and can form an opening by exposure in a later step, and a polymer compound (at least by applying energy such as exposure). It has a three-layer structure of (A) a reactive polymer precursor layer capable of producing a graft polymer) and (B) an insulating resin composition layer capable of producing a graft polymer on the surface thereof.
In the present specification, “photosensitive resin structural material layer” is referred to as “photosensitive structural material layer”, and “(A) reactive polymer precursor layer” formed on the photosensitive structural material layer is referred to as “ (A) layer ”or“ polymer precursor layer ”and“ (B) insulating resin composition layer ”may be referred to as“ (B) layer ”or“ insulating film ”, respectively.
In addition, in order to protect the layer which has various functions which the laminated body which consists of a photosensitive structural material layer and the said (A) layer and (B) layer formed on it by use, of a laminated body A protective layer can be provided on at least one of the surface of the photosensitive structural material layer and the layer (A).
In the present invention, first, an insulating resin composition layer (B) that becomes an insulating film is formed on the surface of the photosensitive structural material layer, and a graft polymer that is bonded to the layer (B) is formed on the surface. (A) It has a reactive polymer precursor layer sequentially.
In the present invention, “sequentially” means that these layers are present on the support in the order described, but other layers provided as desired, for example, an adhesive layer, a cushion layer, etc. It does not deny existence.
Hereinafter, each layer which comprises the laminated body for printed wiring boards of this invention is demonstrated one by one.

[Photosensitive resin structural material layer]
The structural material layer in the laminate of the present invention is disposed on a substrate on which a conductive layer has been formed in advance, and a conductive layer newly formed on the surface of the laminate and the conductive layer previously formed on the substrate. In addition to functioning as an insulating layer, it is made of a resin having a characteristic that an opening for forming a circuit connecting the conductive layers can be easily formed by exposure.
As described above, in the present invention, the base material on which the photosensitive resin structural material layer according to the present invention is formed is referred to as a support, and here, the substrate on which the conductive layer is previously formed corresponds to the support. . Moreover, when this photosensitive resin structural material layer is formed on the resin film which is a support base material, the said resin film corresponds to a support body.
As the photosensitive resin for forming the structural material layer, any resin material can be used as long as the exposed area can be easily removed and a high-definition opening can be formed when exposed and developed at an appropriate wavelength. Examples of such resins include resins described in “Basics and practical use of photosensitive resins” (CMC Technical Library, CM Publishing Co., Ltd., 2001). Among these, a photosensitive polyimide resin and a photosensitive epoxy resin are typical examples from the viewpoint of having insulating properties necessary as an internal component of the multilayer substrate.

(Photosensitive polyimide resin)
A polyimide or a precursor thereof, which itself has photo-patterning properties, is called photosensitive polyimide, and is used for a semiconductor surface protective film or the like.
Several methods for imparting photosensitivity are known for photosensitive polyimide. Typical examples include those prepared by converting the polyamic acid into an ester with hydroxy acrylate as proposed in JP-B-55-41422, and polyamides as proposed in JP-A-54-145794. A compound in which an acid such as amino acrylate is blended and a photosensitive group is introduced by a salt bond is known, and any of them can be used as the structural material layer material of the present invention.
Among them, from the viewpoint of being photosensitive and capable of forming a pattern with high sensitivity by exposure and having a low dielectric constant, a photosensitive polyimide composition described in JP-A-2005-115249 described in detail below. Is preferably used.

  This photosensitive polyimide composition is formed by combining a polyimide precursor with a crosslinking component having a specific thermally decomposable linking group, and a polyimide precursor compound represented by the following general formula (I): It contains a divinyl ether compound having a thermally decomposable group represented by (II) and a photoacid generator.

In the formula, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, and R ³ represents a single bond or a divalent organic group. X represents a divalent thermally decomposable organic group.

  Moreover, in order to form a photosensitive structural material layer with such a polyimide composition, a polyimide precursor compound represented by the above general formula (I) and a thermally decomposable group represented by the above general formula (II) are used. What is necessary is just to apply | coat and dry the photosensitive polyimide composition containing the divinyl ether compound which has, and a photo-acid generator, and to shape | mold into a film form. The photosensitive structural material layer thus obtained can be image-wise exposed and then alkali-developed to form a positive pattern, and then the pattern is heated to form a thermally decomposable organic group. By decomposing, it is possible to form micropores in the exposed region, which is useful as the structural material layer material of the present invention.

That is, in such a polyester composition, when the structural material layer is formed, the compound represented by the general formula (II) (divinyl ether compound) is heated in the resin of the component (I) by heat drying following the coating film. It undergoes an addition reaction with a carboxyl group (and a hydroxy group) to cause crosslinking by an acetal group. By this crosslinked structure, the dissolution inhibiting function of the formed film is expressed.
Thereafter, when imagewise exposure according to a desired pattern is performed, in the exposed portion, the photoacid generator contained in the film is decomposed to generate an acid, and this acid introduces an acid introduced as necessary. The acetal cross-linking portion that had developed the dissolution inhibiting function is decomposed together with the decomposition group, and the original function of the carboxyl group (and hydroxy group) in the resin is exhibited, and sufficient developability for an alkaline developer is exhibited. It will be. Therefore, a pattern with high sharpness is formed by scanning exposure using digital data of a computer.
A heating process is performed after forming the pattern containing this polyimide precursor. Here, by heating to 200 ° C. to 450 ° C., the polyimide precursor is cyclized and converted to polyimide, a polyimide pattern having excellent heat resistance is fixed, and a crosslinkable thermally decomposable organic group. When the X (divalent thermally decomposable organic group) portion in the compound represented by the general formula (II) is decomposed, fine pores are formed in the portion.

That is, according to this polyimide resin composition, formation of a crosslinked structure necessary for image formation, immobilization of a polyimide resin pattern excellent in heat resistance, pattern formation by three simple steps of imagewise exposure, development, and heating. All of the hole formation necessary for lowering the dielectric is achieved. With this function, fine voids are formed simultaneously with pattern formation, and a patterned low dielectric constant polyimide suitable for an insulating film is obtained.
This composition is described in detail in paragraphs [0018] to [0040] of JP-A-2005-115249, and these materials can be suitably applied as the structural material layer forming material of the present invention.

(Photosensitive epoxy resin)
The photosensitive epoxy resin that can be used in the present invention is an epoxy resin that also has a photo-patterning property by itself, and is used for a surface protective film of a semiconductor or the like.
Preferred examples of the photosensitive epoxy resin include those described in JP-A-2002-69159 and JP-A-2005-38906.
Specifically, for example, (a) 40 to 70 parts by weight of a polyfunctional epoxy resin, (b) 30 to 60 parts by weight of a resin having a phenolic hydroxyl group, and 100 parts by weight of the total amount of the components (a) and (b). In contrast, (c) a photosensitive epoxy resin composition containing 1 to 10 parts by weight of a cationic photopolymerization initiator, and at least the component (b) includes a photosensitive epoxy resin composition having an alicyclic structure.

The exposure of the photosensitive epoxy resin can be performed under the same conditions as the polyimide resin.
Moreover, as a developing solution used for development after exposure of the photosensitive epoxy resin composition, a water-soluble organic solvent having a boiling point of 100 ° C. or higher 100 to 500 ml / l, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide A mixed aqueous solution of 1 to 20 g / l of an alkali component selected from sodium carbonate and the like is preferable.
Here, by adding a water-soluble organic solvent having a boiling point higher than that of water to the developer, it is possible to adjust a developer that is nonflammable and exhibits higher developability than an alkali developer. As such a water-soluble high-boiling organic solvent, alcohols such as 2-butoxyethanol, 2,2′-butoxymethoxyethanol, and 2,2′-butoxyethoxyethanol can be preferably used.

The photosensitive structural material layer according to the present invention is not only used as a base of a laminate until the laminate of the present invention is brought into contact with a predetermined substrate and used for forming a printed wiring board, but also conductive. It functions as an interlayer insulating layer between the substrate on which the layer is formed and the patterned conductive layer formed on the surface of the laminate of the present invention.
From such a viewpoint, the thickness of the photosensitive structural material layer is generally 2 to 200 μm, more preferably 5 to 50 μm, and still more preferably 10 to 30 μm. If the structural material layer is too thick, when the wiring is actually formed using this laminate, particularly when the laminate is laminated on a predetermined substrate or wiring, the handling property and the high definition of the opening are high. May cause problems with proper formation.
By making the width of the structural material layer about 5 mm longer than the width of the insulating film or polymer precursor layer, when performing lamination with other layers, it is possible to prevent the resin adhesion of the laminate portion, In addition, advantages such as easy peeling of the support base film during use can be obtained.

[(A) Reactive polymer precursor layer]
In the reactive polymer precursor layer, a compound (polymerizable compound) that can generate a graft polymer by applying energy such as exposure, or a cross-linked structure between adjacent layers by applying energy is formed. It contains a polymer precursor such as a compound that can improve the adhesion. The polymer compound produced by these reactive compounds (hereinafter referred to as a graft polymer as appropriate) adheres a conductive material, so that the polymer precursor can form a polymerization reaction or a crosslinked structure. In order to adhere a partial structure necessary for bonding to the insulating resin composition layer, for example, “unsaturated double bond capable of radical polymerization” and a conductive material described later to the graft polymer. It is preferable to use a compound having both the necessary “functional group capable of interacting with the conductive material”.

(Polymerizable compound)
Typical examples of the polymer precursors described above include polymerizable compounds capable of undergoing a polymerization reaction. The polymerizable compound is a compound having an unsaturated double bond capable of radical polymerization in the molecule.
Examples of the functional group containing “radical polymerizable unsaturated double bond” include a vinyl group, a vinyloxy group, an allyl group, an acryloyl group, and a methacryloyl group. Among these, the acryloyl group and the methacryloyl group are highly reactive, and good results are obtained.
As the unsaturated compound capable of radical polymerization, any compound having a radical polymerizable group can be used. For example, a monomer having an acrylate group, a methacrylate group, or a vinyl group, a macromer, a polymerizable unsaturated group. Oligomers and polymers having groups can be used.
Further, as another embodiment of the polymer precursor, an oligomer or polymer compound having a reactive active group in the molecule, for example, an epoxy group, an isocyanate group, an active group in an azo compound, or a crosslinking agent and a crosslinking property Examples include combinations with compounds.

The polymer precursor further needs to have a functional group capable of interacting with the conductive material, which is a partial structure to which the conductive material can be attached.
The functional group capable of interacting with the conductive material is a functional group having a positive charge such as ammonium or phosphonium, or a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group. Examples thereof include acidic groups that can be dissociated into negative charges. In addition, nonionic polar groups such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, and a cyano group can also be used.
Examples of the functional group having an affinity for the conductive material include a hydrophilic group or a functional group capable of interacting with the electroless plating catalyst or its precursor.

  If the polymer precursor, which is an essential component in the reactive polymer precursor layer (A) according to the present invention, is described in detail by taking a polymerizable compound as a representative example as an example, radical polymerization is possible. The polymerizable compound having such an unsaturated double bond and having a functional group capable of interacting with the conductive material may be a low molecule or a polymer. In the case of a polymer, the average molecular weight is selected in the range of 1,000 to 500,000. Such a polymer can be obtained by methods such as addition polymerization such as normal radical polymerization and anionic polymerization, and polycondensation.

  Specifically, in the present invention, a compound having an unsaturated double bond capable of radical polymerization (hereinafter appropriately referred to as a polymerizable unsaturated group) and a functional group capable of interacting with a conductive material. From the viewpoint of easy adhesion and adsorption of metal ions or metal salts and easy removal of unreacted substances after the grafting reaction, hydrophilic polymers and hydrophilic macromers having a hydrophilic group that is a polar group Hydrophilic monomers are preferred.

-Hydrophilic monomer-
Specific examples of the hydrophilic monomer that can be used in the polymer precursor layer in the present invention include, for example, the following JP-A monomer previously proposed by the applicant of the present application.
For example, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt, Vinyl sulfonic acid or its alkali metal salt and amine salt, styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and amine salt, 2-acrylamido-2-methylpropanesulfonic acid or alkali metal salts and amine salts thereof, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or salts thereof, 2-dimethylaminoethyl (meta Acrylate or its hydrohalide, 3-trimethylammoniumpropyl (meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) Ammonium chloride and the like can be used. In addition, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) ) Acrylate is also useful.

-Hydrophilic macromonomer-
The method for producing a macromonomer that can be used in the present invention is described in, for example, Chapter 2 of “Macromonomer Chemistry and Industry” (Editor, Yuya Yamashita) published on September 20, 1999 by the IP Publishing Bureau. Various production methods have been proposed in “Synthesis”.
Particularly useful hydrophilic macromonomers that can be used in the present invention include macromonomers derived from carboxy group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, and vinylsterene sulfone. Sulfonic acid macromonomer derived from monomer of acid and its salt, (meth) acrylamide, N-vinylacetamide, N-vinylformamide, amide macromonomer derived from N-vinylcarboxylic amide monomer, hydroxyethyl Macromonomers derived from hydroxyl group-containing monomers such as methacrylic acid, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol Macromonomers derived from alkoxy group or ethylene oxide group-containing monomers such Lumpur acrylate. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromonomer of the present invention.
Among these hydrophilic macromonomers, useful ones have a molecular weight in the range of 250 to 100,000, and a particularly preferable range is 400 to 30,000.

-Hydrophilic polymer having a polymerizable unsaturated group-
The hydrophilic polymer having a polymerizable unsaturated group is a radically polymerizable group-containing hydrophilic polymer in which an ethylene addition polymerizable unsaturated group such as a vinyl group, an allyl group or a (meth) acryl group is introduced in the molecule. Point to. This radical polymerizable group-containing hydrophilic polymer needs to have a polymerizable group at the main chain end and / or side chain, and preferably has a polymerizable group at both of them. Hereinafter, a hydrophilic polymer having a polymerizable group (at the main chain end and / or side chain) is referred to as a radical polymerizable group-containing hydrophilic polymer.

  Such a radically polymerizable group-containing hydrophilic polymer can be synthesized by a known method. Such a synthesis method is described in detail, for example, in paragraphs [0149] to [0152] of JP-A-2005-37881 previously filed by the applicant of the present application, and the description also applies to the present invention. be able to.

When a macromonomer or a polymer is used as the polymerizable compound, it is easy to prepare a polymerizable compound-containing liquid composition having a viscosity suitable for layer formation by a coating method. In the laminate of the present invention, (A) a reactive polymer precursor layer is easily formed on the structural material layer or on the (B) insulating resin composition layer described later by applying and drying be able to.
On the other hand, when a hydrophilic monomer is used as the polymerizable compound, it is preferable to use a binder or the like in order to form a stable coating film in the reactive polymer precursor layer (A), or It is preferable to stabilize the layer (A) by coating a low-viscosity coating film made of a liquid composition with a protective layer described in detail below.

From these facts, for example, when a macromonomer or polymer that is a polymerizable compound is used as the polymer precursor, the (A) reactive polymer precursor layer having a uniform film thickness can be formed. It can be seen that a uniform graft polymer formation region is formed. Therefore, when the laminate of the present invention is formed using a macromonomer or a polymer as the polymerizable compound, a conductive layer having excellent conductivity and excellent uniformity can be easily obtained by using the laminate. A printed wiring board formed by the method can be obtained.
As described above, from the viewpoint of manufacturability, a macromonomer or a polymer is used as a polymerizable compound, and these solutions are applied to an insulating film surface made of, for example, an epoxy resin and dried (A) a reactive polymer. Most preferably, a precursor layer is formed.
The polymer precursor represented by these polymerizable compounds is preferably contained in an amount of about 5 to 100% by mass in the nonvolatile component constituting the layer (A), and more preferably in the range of 30 to 100% by mass. .

(Other components that can be used in the polymer precursor layer)
As long as the (A) polymer precursor layer does not impair the effects of the present invention, in addition to the polymerizable compound, depending on the purpose, for example, a binder, a plasticizer, a surfactant, a viscosity for improving film properties Various compounds such as a regulator can be contained.
(binder)
The binder is used for forming the polymer precursor layer (A) together with the polymerizable compound which is the polymer precursor, and is useful for improving the film property. In the case where the polymerizable group compound can form a layer alone, it is not particularly necessary. However, in order to use a monomer having a low viscosity as the polymerizable compound, it is preferably contained from the viewpoint of improving the layer formability. Moreover, it is preferable to contain a binder also in the meaning which adjusts the physical property of the graft polymer layer finally formed. The binder for this purpose is not particularly limited as long as it is mixed with a polymerizable group-containing hydrophilic compound and forms a film, but an oligomer or polymer having a molecular weight of 500 or more is preferable. Since the binder polymer is generally removed during purification after the graft polymer is formed, a binder polymer that is soluble or dispersible in a cleaning solution such as water, alkaline aqueous solution, or organic solvent used during purification should be selected. Is preferred.
These polymers include (meth) acrylate polymers such as polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polybutyral, polyvinylpyrrolidone, polyethylene oxide, polyethyleneimine, polyacrylamide, carboxymethylcellulose, hydroxyethylcellulose, sesulose polymers, In addition to synthetic polymers such as, natural hydrophilic polymers such as gelatin, starch, gum arabic, and sugar can be used.
When using a binder together, the content is preferably 0 to 95% by mass, more preferably 0 to 70% by mass in terms of solid content.

(Plasticizer, surfactant, viscosity modifier)
These compounds (A) improve the coating surface properties during the formation of the coating of the reactive polymer precursor layer, or provide cracking to the coating when it is folded in a film state. Used for suppression. As the plasticizer, surfactant, and viscosity modifier, commonly used known materials are used.

(Formation of reactive polymer precursor layer)
(A) The reactive polymer precursor layer is a coating solution prepared by dissolving the above-described components in an appropriate solvent, or a coating solution adjusted to a uniform solution state by compatibilizing each component with each other. It is formed by applying and drying the liquid on the structural material layer or on an insulating film (B) described later.
As the solvent, water and an organic solvent are used. As the organic solvent, either a hydrophilic solvent or a hydrophobic solvent can be used, but a solvent having a high affinity for water is particularly useful. Specifically, alcohol solvents such as methanol, ethanol and 1-methoxy-2-propanol, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran, and nitrile solvents such as acetonitrile are preferable.
The solid content concentration of the coating solution is preferably 0.1 / 80% by mass.
Application is performed by a conventional method, for example, blade coating method, rod coating method, squeeze coating method, reverse roll coating method, transfer coat coating method, spin coating method, bar coating method, air knife method, gravure printing method, spray coating. And a known coating method.

The thickness of the reactive polymer precursor layer is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.3 μm to 5 μm. In this range, the thickness of the graft polymer layer to be formed thereafter becomes a suitable range, and in the subsequent step, for example, even when a conductive material is adhered, excellent adhesion between the conductive material can be ensured. .
After forming the polymer precursor layer, the thickness of the graft polymer layer formed by applying energy such as exposure is preferably in the range of 0.05 μm to 1.5 μm, and preferably in the range of 0.1 μm to 1.0 μm. Further preferred. Therefore, even if the thickness of the polymer precursor layer is increased to more than 10 μm, the material that does not participate in the formation of the graft polymer increases, which not only increases the cost, but also makes it difficult for the exposure light source to reach the deep part. This causes many problems such as difficulty in removing unnecessary graft polymer precursor materials.

[(B) Insulating resin composition layer]
In the formation of the insulating resin composition layer in the present invention, a known insulating resin that has been used as a conventional multilayer laminate, a build-up substrate, or a flexible substrate can be used. These resins are composed of a thermosetting resin, a thermoplastic resin, or a resin mixture thereof. The insulating resin composition layer according to the present invention is composed of the resin composition, and the term “consisting of the resin composition” is a concept including the resin composition itself and a cured product thereof. In the present invention, these resins can be used as they are, but from the viewpoint that the surface chemical bond forming reaction with the (A) reactive polymer precursor layer provided in the vicinity can be easily performed, these insulations are used. It is preferable to use a resin containing a polymerization initiator. In addition, a polyfunctional acrylate monomer may be added for the purpose of increasing the strength of the surface chemical bond generation reactivity or the insulating resin composition layer. In addition, inorganic or organic particles may be added as other components in order to increase the strength of the insulator layer or improve electrical characteristics. The “insulating resin” in the present invention means a resin having an insulating property that can be used for a known insulating film, and even if it is not a perfect insulator, Any resin having an insulating property corresponding to the above can be applied to the present invention.
Hereinafter, each component used for the insulating resin composition layer which can be used for this invention is demonstrated in order.

Specific examples of the thermosetting resin that can be used in the (B) insulating resin composition layer according to the present invention include, for example, epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, and isocyanates. Based resins and the like.
Examples of the epoxy resin include cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, dicyclo Examples thereof include pentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, and alicyclic epoxy resins. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.

  Examples of the polyolefin resin include polyethylene, polystyrene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, cycloolefin resin, and copolymers of these resins.

Further, the epoxy resin will be described in detail.
In the present invention, (B) the epoxy resin constituting the insulating resin composition layer is composed of (a) an epoxy compound having two or more epoxy groups in one molecule and (b) a functional group that reacts with the epoxy group in one molecule. It consists of a reaction product with a compound having two or more. The functional group in (b) is selected from functional groups such as a carboxyl group, a hydroxyl group, an amino group, and a thiol group.

(A) As an epoxy compound (including what is called an epoxy resin) having two or more epoxy groups in one molecule, an epoxy compound having 2 to 50 epoxy groups in one molecule is preferable. More preferably, the epoxy compound has 2 to 20 epoxy groups in one molecule. Here, the epoxy group should just be a structure which has an oxirane ring structure, For example, a glycidyl group, an oxyethylene group, an epoxy cyclohexyl group etc. can be shown. Such polyvalent epoxy compounds are widely disclosed in, for example, published by Masaki Shinbo “Epoxy Resin Handbook” published by Nikkan Kogyo Shimbun (1987), and these can be used.
Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin. These resins may be used alone or in combination of two or more.

(B) As a compound having two or more functional groups that react with an epoxy group in one molecule, a polyfunctional carboxylic acid compound such as terephthalic acid, a polyfunctional hydroxyl compound such as a phenol resin, an amino resin, 1, 3, 5 Mention may be made of polyfunctional amino compounds such as triaminotriazine.
The resin composition of the present invention may contain an epoxy resin curing agent. For example, polyfunctional phenols, amine Louis, imidazole compounds, acid anhydrides, organophosphorus compounds, and halides thereof may be used, but those that do not inhibit chemical reaction with the polymer precursor layer are preferably used. Moreover, you may mix | blend a hardening accelerator with the insulating resin composition of this invention as needed. Representative curing accelerators include, but are not limited to, tertiary amines, imidazoles, and quaternary ammonium salts.

  Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like. Other thermoplastic resins include (1) 1,2-bis (vinylphenylene) ethane resin (1,2-Bis (vinylphenyl) ethane) or a modified resin of this with a polyphenylene ether resin (Satoru Ama et al., Journal of Applied). Polymer Science Vol. 92, 1252-1258 (2004)). (2) Liquid crystalline polymers, specifically Kuraray Bexter. (3) Fluororesin (PTFE).

(Mixing of thermoplastic resin and thermosetting resin)
The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. This is performed for the purpose of compensating for each defect and producing a superior effect. For example, thermoplastic resins such as polyphenylene ether (PPE) have a low resistance to heat, and are therefore alloyed with thermosetting resins. For example, it is used for alloying PPE with epoxy and triallyl isocyanate, or alloying PPE resin into which a polymerizable functional group is introduced and other thermosetting resins. Cyanate ester is a resin having the most excellent dielectric properties among thermosetting, but it is rarely used alone and is used as a modified resin such as epoxy resin, maleimide resin, and thermoplastic resin. Details thereof are described in Electronic Technology No. 2002/9, P35. A thermosetting resin containing an epoxy resin and / or a phenol resin and a thermoplastic resin containing a phenoxy resin and / or polyether sulfone (PES) are also used to improve dielectric properties.

(Compound having a polymerizable double bond)
A necessary compound can be added to the insulating film according to the purpose of use. As such a compound, there is a compound having a radical polymerizable double bond. The compound having a radical polymerizable double bond is an acrylate or methacrylate compound. The acrylate compound [(meth) acrylate] that can be used in the present invention is not particularly limited as long as it has an acryloyl group that is an ethylenically unsaturated group in the molecule, but is curable and the hardness of the formed intermediate layer. From the viewpoint of improving the strength, a polyfunctional monomer is preferable.

  The polyfunctional monomer that can be suitably used in the present invention is preferably an ester of a polyhydric alcohol and acrylic acid or methacrylic acid. Examples of polyhydric alcohols include ethylene glycol, 1,4-cyclohexanol, pentaerythritol, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, polyurethane polyol and polyester polyol. . Of these, trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyol are preferable. The intermediate layer may contain two or more types of polyfunctional monomers. The polyfunctional monomer is one containing at least two ethylenically unsaturated groups in the molecule, and more preferably containing three or more. Specific examples include polyfunctional acrylate monomers having 3 to 6 acrylate groups in the molecule, and several acrylic acids in the molecule called urethane acrylate, polyester acrylate, and epoxy acrylate. An oligomer having an ester group and having a molecular weight of several hundred to several thousand can be preferably used as a component of the intermediate layer of the present invention.

Specific examples of acrylates having three or more acrylic groups in the molecule include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Examples thereof include polyol polyacrylates such as hexaacrylate, and urethane acrylates obtained by reaction of polyisocyanates with hydroxyl group-containing acrylates such as hydroxyethyl acrylate. In addition, as a compound having a polymerizable double bond, a thermosetting resin or a thermoplastic resin, for example, an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, methacrylic acid or acrylic acid, A resin obtained by subjecting a part of the resin to (meth) acrylation reaction may be used. Specific examples include (meth) acrylate compounds of epoxy resins.
It is preferable that these insulating resins are 5-100 mass% in conversion of solid content in the composition which forms an insulating resin composition layer.

(Type of polymerization initiator added to the insulating resin composition layer)
As the polymerization initiator that can be used in the insulating resin composition layer (B) in the present invention, either a thermal polymerization initiator or a photopolymerization initiator can be used. As the thermal polymerization initiator, peroxide initiators such as benzoyl peroxide and azoisobutyronitrile, and azo initiators can be used. The photopolymerization initiator may be a low molecule or a polymer, and generally known ones are used.
Examples of the low-molecular photopolymerization initiator include known radicals such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram monosulfide, trichloromethyltriazine, and thioxanthone. Generators can be used. In addition, since sulfonium salts and iodonium salts used as photoacid generators usually act as radical generators upon irradiation with light, they may be used in the present invention. A sensitizer may be used in addition to the radical photopolymerization initiator for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.
As the polymer photoradical generator, polymer compounds having an active carbonyl group in the side chain described in JP-A-9-77891 and JP-A-10-45927 can be used.
The amount of the polymerization initiator to be contained in the insulating resin is selected according to the use of the surface chemical bond generating material to be used, but generally 0.1 to 50% by mass in solid content in the insulating layer. Is preferably about 1.0 to 30.0% by mass.

(Other additives contained in the insulating resin composition layer)
In the layer (B) of the present invention, a composite (composite of resin and other components) is used to enhance the mechanical strength, heat resistance, weather resistance, flame retardancy, water resistance, electrical properties, etc. of the resin coating. Material) can also be used. Examples of the material used for the composite include paper, glass fiber, silica particles, phenol resin, polyimide resin, bismaleimide triazine resin, fluorine resin, polyphenylene oxide resin, and the like.
Further, this insulating resin composition may be filled with a filler used for general wiring board resin materials as necessary, for example, inorganic fillers such as silica, alumina, clay, talc, aluminum hydroxide, calcium carbonate, and cured epoxy. You may mix | blend 1 type, or 2 or more types of organic fillers, such as resin, crosslinked benzoguanamine resin, and a crosslinked acrylic polymer.
Further, the insulating resin composition may contain one or more various additives such as a colorant, a flame retardant, an adhesion imparting agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. It may be added.
When these materials are added, it is preferable to add them in the range of 1 to 200% by mass, and more preferably in the range of 10 to 80% by mass with respect to the resin. When this addition amount is less than 1% by mass, there is no effect of strengthening the above-mentioned properties, and when it exceeds 200% by mass, properties such as strength specific to the resin are lowered. The surface chemical bond generation reaction also does not proceed.

(Insulating resin composition layer shape)
In general, the thickness of the insulating film in the present invention is preferably 5 μm to 1000 μm, and more preferably 5 μm to 300 μm.
From the viewpoint of improving the physical properties of the conductive layer to be formed, the insulating film made of an insulating resin has an average roughness (Rz) measured by JIS B 0601 (1994), 10-point average height method of 3 μm or less. It is preferable to use a certain one, and it is more preferable that Rz is 1 μm or less. If the surface smoothness of the substrate is within the above value range, that is, if there is substantially no unevenness, the circuit is very fine (for example, a circuit pattern with a line / space value of 25/25 μm or less). It is used suitably when manufacturing.
From the same viewpoint, when the wiring is formed on the substrate using the laminate of the present invention, the smoothness of the substrate used is preferably in the above range.

(B) Formation of insulating resin composition layer (B) A coating solution prepared to improve coatability by dissolving the above-described components in a suitable solvent or varnished, or An insulating film forming film is prepared by applying and drying a coating solution, which is prepared by compatibilizing each component with each other, on a structural material layer or the above-described (A) polymer precursor layer. Is formed. The film for forming an insulating film can be used as an insulating film, an adhesive film, and the like for various electronic parts by forming the film to improve the thickness accuracy, improve the handleability and alignment accuracy, and the like.
A general organic solvent is used as the solvent. As the organic solvent, either a hydrophilic solvent or a hydrophobic solvent can be used, but a thermosetting resin and a thermoplastic resin that form an insulating resin composition layer, and a polymer that forms these resins after the reaction. Solvents that dissolve the precursor are useful. Specifically, alcohol solvents such as methanol, ethanol and 1-methoxy-2-propanol, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran, and nitrile solvents such as acetonitrile are preferable. Furthermore, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, ethylene glycol monomethyl ether, tetrahydrofuran and the like can be used.

From the viewpoint of the coating solution or varnish viscosity and workability, coating properties, and drying time and work efficiency with respect to 100 parts by weight of the insulating resin composition. The amount is preferably 5 parts by weight or more and 2000 parts by weight or less, and more preferably 10 to 900 parts by weight.
As a method for preparing the varnish of the resin composition, it can be prepared by using a known method such as a mixer, a bead mill, a pearl mill, a kneader, or a three roll. Various compounding ingredients may be added all at the same time, the order of addition may be set as appropriate, or some compounding ingredients may be added after pre-kneading if necessary. .

Coating on the support for film formation is performed by a conventional method, for example, blade coating method, rod coating method, squeeze coating method, reverse roll coating method, transfer coal coating method, spin coating method, bar coating method, Known application methods such as an air knife method, a gravure printing method, and a spray coating method may be used.
The method for removing the solvent is not particularly limited, but it is preferably performed by evaporation of the solvent. As a method for evaporating the solvent, methods such as heating, decompression, and ventilation are conceivable. Among these, it is preferable to evaporate by heating from the viewpoint of production efficiency and handleability, and more preferable to evaporate by heating with ventilation. For example, by coating on one side of the support described below and drying by heating at 80 ° C. to 200 ° C. for 0.5 to 10 minutes to remove the solvent, a semi-cured and non-sticky film It is preferable to do.

[Adhesive layer, cushion layer]
When forming the laminate for a printed wiring board of the present invention, in order to improve the adhesion with the insulating resin composition layer formed adjacent to the printed wiring board, or to improve the cushioning property at the time of lamination. In order to improve adhesion, an adhesive resin varnish dissolved in a predetermined organic solvent is applied between the base film serving as the protective layer and the insulating resin layer, and then the solvent is removed by heating and / or hot air blowing. It can be dried to form a room temperature solid resin composition, and an adhesive layer or a cushion layer can be produced.
Here, the organic solvent used for the application of the adhesive resin varnish is usually a solvent, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate. Acetic acid esters such as cellosolve, cellosolve such as butylcellosolve, carbitols such as carbitol and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. It can be used alone or in combination of two or more.

[Protective layer]
As a resin film for forming a protective layer, it is preferable to use surface adhesives such as polyethylene, polyvinyl chloride, polyolefins such as polypropylene, polyesters such as polyethylene terephthalate, polyamide, polycarbonate resin sheets, and release paper. Processed paper with controlled properties, copper foil, metal foil such as aluminum foil, and the like.
The thickness of the protective layer (protective film) is generally 2 to 150 μm, more preferably 5 to 70 μm, still more preferably 10 to 50 μm. Further, either the thickness of the protective film or the thickness of the support base film may be thicker than the other.
The protective film may be subjected to a releasing treatment in addition to the matting and embossing.

  In the laminate for a printed wiring board of the present invention, this protective film can be further laminated on either or both of the photosensitive structural material layer surface, the (A) layer surface. After laminating these protective films, for example, they are wound into a roll and stored.

[Manufacture of laminates for printed wiring boards]
The laminate for a printed wiring board of the present invention is formed by first providing the photosensitive structural material layer on a support, and sequentially containing a polymerization initiator in the insulating resin composition thereon (B It is formed by forming an insulating resin composition layer, (A) a polymer precursor layer, and covering the (A) polymer precursor layer with a protective layer. Further, an adhesive layer may be provided between the photosensitive structural material layer and the (A) polymer precursor layer.
Thus, the laminated body for printed wiring boards of this invention is obtained.

In the laminate of the present invention, an initiator-containing insulator is obtained by containing a polymerization initiator in an insulating resin such as an epoxy resin, a polyimide resin, a liquid crystalline resin, or a polyarylene resin on the surface of the photosensitive structural material layer. The main feature is that a polymer precursor layer is provided adjacent to the layer, and this laminate is applied to the surface of any base material or wiring to impart energy. Thus, an insulator layer having desired characteristics and a graft polymer generation region directly bonded to the surface of the insulator layer can be formed. Since this graft polymer is excellent in affinity with a conductive material, a smooth and uniform conductive film can be formed in a desired region according to energy application by using the laminate for a printed wiring board of the present invention. it can.
In addition, since the photosensitive structure material layer can easily form an opening corresponding to the exposure accuracy by exposure and development, it is easy to form a wiring between the formed conductive layer and the conductive film on the substrate. It can be carried out.

In the present invention, by including a polymerization initiator in the insulating resin, the adhesion between the insulator layer and the graft polymer is further strengthened, and a strong adhesion is exhibited.
The reason for this is not clear, but the addition of a polymerization initiator to the insulating resin layer increases the density of surface chemical bonds, and the interaction with the conductive material layer is increased, resulting in improved adhesion. It is considered possible.
In addition, this technique is a wide technique that can be applied to general insulating resins useful in the field of electronic materials such as polyimide and epoxy resin.

[Manufacture of multilayer metal wiring patterns using laminates for printed wiring boards]
The laminate of the present invention can be used for producing a multilayer metal wiring pattern. In the present invention, the wiring pattern includes not only a circuit-like wiring but also a structure for connecting wirings between different layers. As a method for producing a multilayer metal wiring board, first, the protective film of the laminate of the present invention is peeled off, and the photosensitive structural material layer is brought into close contact with the surface of the inner layer circuit board having a conductive film. From the active site generated from the initiator in the insulating film (B), the polymerizable compound in the polymer precursor layer is based on the active point generated from the initiator in the insulating film / A strong chemical bond is generated at the precursor layer interface to form a graft polymer. Thereafter, the unreacted (A) polymer precursor layer is removed, and a conductive material is attached to the generated graft polymer, so that an insulating film and wiring (pattern-shaped) are further formed on the surface of the inner circuit board having the conductive film. A laminate in which a conductive layer is formed can be obtained.
Thereafter, a region in which the via hole is to be formed is exposed and developed to form an opening in the structural material layer made of a photosensitive resin. The opening formed after the development can be filled with a conductive material to connect the conductive layer on the substrate and the conductive layer formed on the insulating resin composition layer.
If desired, heat treatment can be performed to improve the crosslink density in the structural material layer, or depending on the material, fine pores useful for improving insulation can be formed.

Below, the detail of the manufacturing method of the multilayer metal wiring board using the laminated body of this invention is described.
By using the laminate of the present invention, a printed wiring board having excellent characteristics can be easily formed on an arbitrary solid surface. That is, the surface of the insulating resin material layer having a heat resistance and low dielectric constant, such as an epoxy resin, a polyimide resin, a liquid crystal resin, or a polyarylene resin, or a metal film material such as a copper-clad laminate is roughened. It is possible to produce a metal wiring pattern that exhibits high adhesion strength without being changed.

When laminating the laminate of the present invention to an inner circuit board having a patterned metal thin film (substrate having a conductive film), after removing the protective film, the surface of the photosensitive structural material layer is brought into close contact, and if desired, (A) The insulating resin composition layer (insulating film) with a polymer precursor layer that is solid at room temperature is laminated from the protective layer side formed on the surface of the layer while applying pressure and heating.
By laminating under the condition that the resin flow at the time of laminating is equal to or greater than the conductor thickness of the inner layer circuit and half the through-hole depth of the inner layer circuit and / or the surface via hole depth of the inner layer circuit, The resin filling in the through hole of the coating and the inner layer circuit and / or the surface via hole of the inner layer circuit can be performed simultaneously.
In addition, as an inner layer circuit board, glass epoxy used as a board | substrate in the printed wiring board field | area, polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, paper, glass cloth, glass nonwoven fabric, liquid crystal polymer, etc. It is possible to use a substrate with phenolic resin, epoxy resin, imide resin, BT resin, PPE resin, tetrafluoroethylene resin, etc. as the resin, and the circuit surface is roughened in advance. Even if it exists, it does not need to be processed.

Lamination may be batch type or continuous roll type under reduced pressure, and may be laminated on one side or on both sides simultaneously, but it is preferable to laminate on both sides simultaneously. The laminating conditions as described above vary depending on the melt viscosity during heating, the thickness and the through hole diameter, depth and / or surface via hole diameter, and depth of the inner layer circuit board of the composition constituting the room temperature solid insulating resin layer in the present invention. However, in general, the pressure bonding temperature is 70 to 200 ° C., the pressure bonding pressure is 1 to 10 kgf / cm ² , and the lamination is preferably performed under a reduced pressure of 20 mmHg or less. When the through-hole diameter is large and deep, that is, when the plate thickness is large, the resin composition is thick, and lamination conditions at high temperature and / or high pressure are required.

  In general, the inner layer circuit board can be satisfactorily filled with a resin having a thickness of about 1.4 mm or less, and the inner layer circuit board can have a through hole diameter of about 1 mm or less. In addition, the surface smoothness of the resin composition after lamination becomes better as the support base film is thicker, but it is disadvantageous for embedding the resin without voids between the circuit patterns. Therefore, the support base film has a conductor thickness of ± 20 μm. This is true. However, because the conductor thickness of the inner layer circuit is thick, the surface smoothness and thickness of the resin on the pattern are not sufficient, or the inner layer circuit board has large and deep diameters of through-holes and surface via holes, resulting in indentations on the holes. In that case, it is possible to cope with various conductor thicknesses and plate thicknesses by further laminating the multilayer printed wiring board laminate of the present invention thereon. After lamination, the support base film is peeled off after cooling to around room temperature.

  After laminating the laminate for a printed wiring board on the inner layer circuit board, the resin composition in the polymer precursor layer is thermally cured as necessary. The conditions for heat curing differ depending on the type of material of the inner circuit board, the type of resin composition constituting the laminate for the printed wiring board, and the like, and depending on the curing temperature of these forming materials, the condition of thermosetting is 120. It is selected in the range of 20 minutes to 120 minutes at ˜220 ° C. Thereafter, while peeling off the support film, the portion forming the conductive layer is irradiated with actinic rays (for example, electron beam, UV light, etc.) to produce a graft polymer bonded directly to the surface of the insulating film. The light irradiation method may be direct irradiation with a laser or the like, or the pattern mask may be placed in close contact with the polymer precursor layer and irradiated through the pattern mask. Thereafter, unreacted polymerizable compounds not involved in the formation of the graft polymer are removed by development or washing treatment.

  If necessary, the surface of the polymer precursor layer is roughened by a dry method and / or a wet method. Examples of the dry roughening method include mechanical polishing such as buffing and sandblasting, plasma etching, and the like. On the other hand, the wet roughening method includes chemical treatment such as a method using an oxidizing agent such as permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, a strong base or a resin swelling solvent. . In the present invention, sufficient roughening is not necessarily required, and it is sufficient to remove smear generated when the opening is formed in the through hole and / or the via hole.

  Next, a conductive layer is formed in the graft polymer formation region by the method described later, and then a wiring pattern (conductive layer) is formed by using the subtractive method or the semi-additive method described above. Between the conductive layer previously formed on the substrate (inner circuit board) by providing an opening in the structural material layer and the patterned conductive layer formed using the laminate for a printed wiring board of the present invention A multilayer metal wiring pattern can be obtained by forming a wiring connecting the two.

The predetermined via hole portion can be formed after the graft polymer is formed and before or after the conductive material is attached.
Both the positive type and the negative type can be used for the photosensitive structural material layer of the present invention. For example, a photosensitive polyimide resin composition containing a photoacid generator is a positive type, and after exposing the photosensitive structural material layer imagewise, a positive type pattern in which an exposed portion is removed by development is obtained. Form. In addition, the photosensitive epoxy resin composition containing a cationic photopolymerization initiator is a negative type, and after exposing the photosensitive structural material layer imagewise, the exposed portion is cured and left undeveloped by development. A negative pattern is formed with portions removed.
As a light source for pattern exposure used to form an opening in the photosensitive structural material layer, a normal visible light source or UV light source is used. From the viewpoint of material handling. It is preferable to use a UV light source. The wavelength is preferably 400 nm or less, more preferably ultraviolet light having a wavelength of 200 nm or more and 400 or less. High pressure mercury lamp (366 nm), low pressure mercury lamp (254 nm), LD laser having a wavelength in the UV region of 405 ± 10 nm, semiconductor excited solid (YVO 4) laser (355 nm), KrF excimer laser (248 nm), etc. An excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, or an electron beam may be used.
The exposure wavelength at this time is preferably different from the exposure wavelength for producing the graft polymer.

By pattern exposure, in the exposed region of the photosensitive structural material layer, the crosslink is cut by the acid generated from the photoacid generator, so that the resistance to dissolution in an alkali developer in the exposed area is lowered and soluble in the alkali developer. Become.
Developers usable in the method of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide And alkaline aqueous solutions of cyclic amines such as pyrrole and pyrrolidin. Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
In the unexposed area, the alkali-development-resistant characteristics are maintained by the crosslinked structure formed when the photosensitive structural material layer is formed, so this development process removes only the exposed area and forms an opening in the exposed area. The

After passing through the exposure / development process for forming the opening, for example, when the photosensitive polyimide composition is used, a ring-closure reaction occurs in the polyimide precursor, which is heat resistant and strong. As a result, a thermally decomposable organic group present in the photosensitive layer is decomposed to form micropores in the patterned photosensitive layer. These micropores have a nanoscale size, and preferably have a diameter of 1 to 200 nm, more preferably 1 to 100 nm. The presence of such nanoscale fine pores uniformly in the layer achieves a low dielectric constant of the formed polyimide pattern. If the micropores are on the micron (μ) scale, that is, the diameter is about 1 μm or more, it is difficult to achieve a low dielectric constant.
The heating conditions in this vacancy formation step are preferably 200 ° C. and 450 ° C. or less from the viewpoint of the reactivity of the imide ring-closing reaction and the vacancy formation property, and more preferably in the range of 250 to 400 ° C. The heating time is preferably about 10 minutes to 3 hours.
The presence of the pores can be confirmed by observing the cross section of the photosensitive layer with a scanning electron microscope (SEM).

The photosensitive structural material layer thus obtained becomes a polyimide insulating resin layer having a lower dielectric constant than that before heating.
A wiring for connecting circuits between layers is formed by filling the opening formed here with a conductive material. The filling of the conductive material may be performed, for example, by filling conductive fine particles (metal fine particles), preferably by heat treatment, or by performing electroplating as described above.
According to the method of the present invention, an interlayer circuit can be formed with high resolution only in a desired region by ultraviolet exposure. Therefore, according to the method of the present invention, high-definition and high-density wiring can be easily formed, and a multilayer metal wiring pattern suitable as a circuit for mounting can be easily formed.
Moreover, a multilayer printed wiring board can also be manufactured by repeating a plurality of the above forming methods and laminating buildup layers in multiple stages.

Hereinafter, a method for forming a patterned conductive layer on the laminate of the present invention will be described in detail.
(Granting energy)
Formation of the graft polymer in the present invention is performed by irradiation with radiation such as heat or light. As heat, a heater and heating by infrared rays are used. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.

If the entire surface of the insulating film is exposed, a graft polymer is generated on the entire surface, and if pattern exposure is performed, the graft polymer is generated in a pattern only in the exposed region.
By providing a conductive material to the graft polymer to form a conductive film, a conductive film having excellent adhesion to a smooth insulator layer can be obtained.

  High adhesion between the insulating film and the conductive material is as follows. 1. Strong and high-density bond between the insulating film and the graft polymer; The produced graft polymer and the conductive material are exerted by the strong interaction. This is achieved. In order to exhibit these effects, it is important to select a compound that strongly interacts with the graft polymer and the conductive material in addition to adding a polymerization initiator to the insulating film.

Hereinafter, a typical method for attaching the conductive material to the graft polymer will be described.
[Method for imparting conductive material to graft polymer formed on insulator layer surface]
As the step of imparting conductivity to the graft polymer, (1) a step of attaching conductive fine particles to the generated graft polymer, (2) a metal ion or a metal salt is imparted to the generated graft polymer, and then the metal ion Or a step of depositing metal by reducing metal ions in the metal salt, (3) a step of electroless plating by applying an electroless plating catalyst or a precursor thereof to the formed graft polymer, and (4) It is preferably any one selected from a step of applying a conductive monomer and then causing a polymerization reaction to form a conductive polymer layer. Further, these steps (1) to (4) may be combined, and a method such as electroplating may be added to further increase the conductivity. Moreover, you may have a heating process after provision of an electroconductive material.

  In the present invention, among the steps of forming a conductive film by applying a conductive substance to the generated graft polymer, (2) adding a metal ion or metal salt to the generated graft polymer, and then the metal ion or the metal As a method for carrying out the step of precipitating metal by reducing metal ions in the salt, specifically, (2-1) metal ions are adsorbed to a graft polymer comprising a compound having a polar group (ionic group). (2-2) impregnating a graft polymer composed of a nitrogen-containing polymer having a high affinity for a metal salt, such as polyvinylpyrrolidone, polyvinylpyridine, and polyvinylimidazole, with a metal salt or a solution containing the metal salt There is a way to make it.

  (3) In the step of applying electroless plating catalyst or precursor thereof to the generated graft polymer and performing electroless plating, a graft polymer having a functional group that interacts with the electroless plating catalyst or precursor thereof is added. After the formation and application of an electroless plating catalyst or a precursor thereof to the graft polymer, electroless plating is performed to form a metal thin film. Also in this embodiment, since the graft polymer having a functional group that interacts with the electroless plating catalyst or its precursor is directly bonded to the insulating resin composition layer, the formed metal thin film has high conductivity as well as high conductivity. It will show strength and wear resistance. Moreover, a conductive film having a desired thickness can be easily formed by further performing electrolytic plating using the electroless plating film obtained here as an electrode.

  In the present invention, specifically, (1) a step of attaching conductive fine particles to the generated graft polymer (“conductive fine particle attachment step”), (2) a metal ion or a metal salt on the generated graft polymer (“Metal ion or metal salt application step”), and thereafter, a step of reducing metal ions or metal ions in the metal salt to precipitate metal (“metal (fine particle) film formation step”), (3 ) A step of applying an electroless plating catalyst or a precursor thereof to the resulting graft polymer (“electroless plating catalyst application step”) and performing electroless plating (“electroless plating step”), and (4) conductivity. It is preferable that the step be performed by any of the steps of applying a monomer (“conductive monomer applying step”) and causing a polymerization reaction to form a conductive polymer layer (“conductive polymer forming step”). There.

(1) Step of attaching conductive fine particles This method is a step of directly attaching conductive fine particles to the polar group of the graft polymer. The conductive fine particles exemplified below are electrostatically and ionically converted into polar groups. What is necessary is just to make it adhere (adsorb | suck).

The conductive fine particles that can be used in the present invention are not particularly limited as long as they have conductivity, and fine particles made of a known conductive material can be arbitrarily selected and used. For example, fine metal particles such as Au, Ag, Pt, Cu, Rh, Pd, Al, Cr, In ₂ O ₃ , SnO ₂ , ZnO, CdO, TiO ₂ , CdIn ₂ O ₄ , Cd ₂ SnO ₂ , Zn ₂ SnO ₄ , oxide semiconductor fine particles such as In ₂ O ₃ —ZnO, fine particles using a material doped with impurities compatible with these, spinel compound fine particles such as MgInO and CaGaO, and conductivity such as TiN, ZrN, and HfN Suitable examples include nitride fine particles, conductive boride fine particles such as LaB, and conductive polymer fine particles as organic materials.

  When the graft polymer has an anionic polar group, a conductive film is formed by adsorbing conductive particles having a positive charge thereto. Examples of the cationic conductive particles used here include metal (oxide) fine particles having a positive charge. In addition, conductive particles having a negative charge are adsorbed on the graft polymer having a cationic polar group to form a conductive film.

  The particle diameter of the conductive fine particles is preferably in the range of 0.1 nm to 1000 nm, and more preferably in the range of 1 nm to 100 nm. When the particle diameter is smaller than 0.1 nm, the conductivity caused by the continuous contact between the surfaces of the fine particles tends to decrease. On the other hand, when the thickness is larger than 1000 nm, the contact area that interacts and bonds with the functional group whose polarity has been changed is reduced, so that the adhesion between the hydrophilic surface and the particles decreases, and the strength of the conductive region tends to deteriorate. .

(2) A step of applying a metal ion or a metal salt, and then reducing the metal ion or the metal ion in the metal salt to deposit a metal. In the aspect (2) of the conductive substance adhesion step of the present invention , A step of applying a metal ion or metal salt to the graft polymer (metal ion or metal salt applying step), a step of reducing the metal ion or metal ion in the metal salt to deposit a metal (metal (fine particle) film formation By performing (Process), a conductive pattern is formed. That is, in the embodiment (2), the metal ion such as a hydrophilic group of the graft polymer or the functional group capable of attaching the metal salt adheres (adsorbs) the metal ion or metal salt depending on the function. Subsequently, the adsorbed metal ions and the like are reduced, so that a metal simple substance is deposited in the graft polymer region, and depending on the deposition mode, a metal thin film is formed, or a metal fine particle adhesion layer formed by dispersing metal fine particles Will be formed.

  As a result, a metal (fine particle) film is formed. When a metal thin film (continuous layer) is formed, a region with particularly high conductivity is formed. Here, after adsorbing the fine particles, a heating step can be performed for the purpose of improving conductivity.

The “metal ion or metal salt application step” and the “metal (fine particle) film formation step” in the aspect (2) will be described in detail.
<Metal ion or metal salt application step>
[Metal ions and metal salts]
A metal ion and a metal salt are demonstrated.
In the present invention, the metal salt is not particularly limited as long as it is dissolved in a suitable solvent for imparting to the graft polymer formation region and can be dissociated into a metal ion and a base (anion). 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 Ag, Cu, Al, Ni, Co, Fe, and Pd. Ag is preferably used as the conductive film and Co is preferably used as the magnetic film.

[Method of applying metal ions and metal salts]
When a metal ion or a metal salt is applied to the graft polymer formation region, when the graft polymer has an ionic group and a method of adsorbing the metal ion to the ionic group is used, the above metal salt is used in an appropriate solvent. The solution containing the metal ions dissolved and dissociated in (1) may be applied to the insulating resin layer in which the graft polymer is present, or the film having the graft polymer may be immersed in the solution. By contacting a solution containing metal ions, metal ions can be ionically adsorbed to the ionic group. From the viewpoint of sufficiently performing these adsorptions, the metal ion concentration or metal salt concentration of the solution to be contacted is preferably in the range of 1 to 50% by mass, and more preferably in the range of 10 to 30% by mass. preferable. The contact time is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.

<Metal (fine particle) film formation process>
[Reducing agent]
In the present invention, the metal salt existing by adsorbing or impregnating the graft polymer, or the reducing agent used to reduce the metal ions and form a metal (fine particle) film, the used metal salt compound is reduced. However, there is no particular limitation as long as it has physical properties for depositing metal, and examples thereof include hypophosphite, tetrahydroborate, and hydrazine.
These reducing agents can be appropriately selected in relation to the metal salt and metal ion to be used. For example, when a silver nitrate aqueous solution or the like is used as the metal salt aqueous solution for supplying the metal ion or metal salt, tetrahydroboron is used. When sodium acid uses an aqueous palladium dichloride solution, hydrazine is preferred.

  As the method of adding the reducing agent, for example, after adding metal ions or metal salts to the surface of the insulating resin layer on which the graft polymer exists, the surface is washed with water to remove excess metal salts and metal ions, A method of immersing an insulating resin layer provided with water in water such as ion exchange water and adding a reducing agent thereto, a method of directly applying or dripping a reducing agent aqueous solution having a predetermined concentration on the surface of the insulating resin layer, etc. Is mentioned. Moreover, as an addition amount of a reducing agent, it is preferable to use an excessive amount equal to or more than the metal ion, and more preferably 10 times equivalent or more.

  The presence of a uniform and high-strength metal (fine particle) film by the addition of a reducing agent can be visually confirmed by the metallic luster of the surface, but using a transmission electron microscope or an AFM (atomic force microscope) By observing the surface, the structure can be confirmed. The metal (fine particle) film can be easily formed by a conventional method, for example, a method of observing the cut surface with an electron microscope.

[Relationship between polarity of functional group of graft polymer and metal ion or metal salt]
If the graft polymer has a functional group having a negative charge, a metal ion having a positive charge is adsorbed on the graft polymer, and the adsorbed metal ion is reduced to form a simple metal (metal thin film or metal fine particle). A depositing region is formed. In addition, when the graft polymer has an anionic property such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group as a hydrophilic functional group as described in detail above, the graft polymer selectively has a negative charge. A metal ion having a positive charge is adsorbed here, and the adsorbed metal ion is reduced to form a metal (fine particle) film region (for example, a wiring).
On the other hand, when the graft polymer chain has a cationic group such as an ammonium group described in JP-A-10-296895, it selectively has a positive charge, and a solution containing a metal salt therein, Alternatively, a metal (fine particle) film region (wiring) is formed by impregnating a solution in which a metal salt is dissolved and reducing metal ions in the impregnated solution or metal ions in the metal salt.
It is preferable from the viewpoint of durability that these metal ions are bonded in the maximum amount that can be imparted (adsorbed) to the hydrophilic group on the hydrophilic surface.

  As a method for imparting metal ions to a hydrophilic group, a method in which a solution in which metal ions or metal salts are dissolved or dispersed is applied to the surface of the graft polymer, and the surface of the graft polymer is immersed in these solutions or dispersions. The method etc. are mentioned. In both cases of application and immersion, the contact time between the solution or dispersion and the surface of the graft polymer because an excessive amount of metal ions is supplied and introduced by sufficient ionic bonds between the hydrophilic groups. Is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.

The metal ion is not limited to one type, and a plurality of types can be used in combination as required. In order to obtain desired conductivity, a plurality of materials can be mixed and used in advance.
In the conductive film formed in the present invention, it is confirmed from the surface observation and cross-sectional observation by SEM and AFM that the metal fine particles are firmly dispersed in the surface graft film. The size of the metal fine particles to be produced is about 1 μm to 1 nm in particle size.

The conductive film produced by the above method may be used as it is when the metal fine particles are densely adsorbed and apparently form a metal thin film, but from the viewpoint of ensuring efficient conductivity. It is preferable to further heat-treat the formed pattern.
The heating temperature in the heat treatment step is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably about 200 ° C. The heating temperature is preferably 400 ° C. or lower in consideration of the processing efficiency, the dimensional stability of the photosensitive constituent material layer, and the insulating resin layer. In addition, the heating time is preferably 10 minutes or more, and more preferably about 30 minutes to 60 minutes. Although the mechanism of action by the heat treatment is not clear, it is considered that the conductivity is improved when some adjacent metal fine particles are fused to each other.

(3) Method of applying electroless plating catalyst or precursor thereof and performing electroless plating Next, “electroless plating catalyst application step” and “electroless plating catalyst application step” in the aspect (3) of the conductive material application step of the present invention and “ The “electroless plating process” will be described. In the aspect (3) of the conductive film forming step in the present invention, the graft polymer has an interactive group that interacts with the electroless plating catalyst or a precursor thereof, and the electroless plating catalyst or the precursor thereof. A conductive film is formed by sequentially performing a step of applying (electroless plating catalyst etc. applying step) and a step of forming a metal thin film by performing electroless plating (electroless plating step). That is, in the aspect of (3), the graft polymer having a functional group (that is, a polar group) that interacts with the electroless plating catalyst or its precursor interacts with the electroless plating catalyst or its precursor, A metal thin film is formed by the electroless plating process.

<Application process for electroless plating catalyst>
In this step, an electroless plating catalyst or a precursor thereof is imparted to the graft polymer generated in the surface grafting step.
[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 the metal colloid whose charge is adjusted in this way interacts with the interactive group (polar group) of the graft polymer. By doing so, a metal colloid (electroless plating catalyst) can be attached to the graft polymer. Moreover, what adsorb | sucked these to various inorganic components may be used. In this case, the inorganic components include colloidal silica, calcium carbonate, magnesium carbonate, magnesium oxide, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, mica, etc., as well as alumina and carbon. Any fine powder may be used. Further, the size of the fine powder at this time is preferably an average particle size of 0.01 to 1.0 μm.

[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 that is the electroless plating catalyst precursor is applied to the substrate in the step (b) and then converted into a zero-valent metal by a reduction reaction before being immersed in the electroless plating bath. Alternatively, the electroless plating 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.

In practice, the metal ion that is the electroless plating precursor is imparted to the graft polymer 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 , MCl _n , 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 Ag ion, Cu ion, Al ion, Ni ion, Co ion, Fe ion, and Pd ion, and Ag ion and Pd ion are preferable in terms of catalytic ability.

  As a method of applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor to a graft polymer, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is dissolved in an appropriate solvent. Then, a solution containing dissociated metal ions is prepared, and the solution is applied to the surface of the insulating resin layer where the graft polymer is present, or a laminate having an insulating resin layer having the graft polymer in the solution is prepared. What is necessary is just to immerse. By contacting a solution containing a metal ion, a metal ion is attached to an interactive group of the graft polymer by using an ion-ion interaction or a dipole-ion interaction, The active region can be impregnated with metal ions. From the viewpoint of sufficiently performing such adhesion 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%. The contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour.

Next, the plating catalyst solution remaining in the portion where the wiring pattern is not formed is removed by washing. The immature region of the graft polymer cannot fix the plating catalyst, and the plating catalyst solution is removed. Next, electroless plating is performed on this, so that electroless plating is performed only on the portion where the wiring pattern conductor layer is to be formed, so that the conductor layer is formed and a multilayer printed wiring board can be manufactured.
After the conductor layer is formed in this way, the thermosetting resin is cured by annealing at 120 to 220 ° C. for 20 to 120 minutes as necessary, and the peel strength of the conductor layer is further improved. It can also be made.

<Electroless plating process>
In this step, a conductive film (metal film) is formed by performing electroless plating on the insulating resin layer to which the electroless plating catalyst or the like has been applied from the electroless plating catalyst or the like application step. That is, by performing electroless plating in this step, a high-density conductive film (metal film) is formed on the graft polymer obtained in the above step. The formed conductive film (metal film) has excellent conductivity and adhesion.

[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 electroless plating in this step is, for example, after removing the excess electroless plating catalyst (metal) by washing the substrate provided with the electroless plating catalyst obtained in the electroless plating catalyst application step, etc. It is performed by immersing in an electroless 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 is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is attached to or impregnated with the graft polymer, the substrate is washed with water to remove an excess precursor. After removing the body (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.
As the types of metals used in the electroless plating bath, copper, tin, lead, nickel, gold, palladium, and rhodium are known, and among these, copper and gold are particularly preferable from the viewpoint of conductivity.
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. Moreover, the electroless plating bath of palladium 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 conductive film (metal film) 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, or the like. From the viewpoint of conductivity, the thickness is preferably 0.1 μm or more, and more preferably 3 μm or more. In addition, the immersion time in the plating bath is preferably about 1 minute to 1 hour, and more preferably about 1 minute to 20 minutes. In the case where electroplating is performed in the next step to obtain conductivity, the electroconductive plating may be provided with conductivity so that the thickness of the electroconductive plating can withstand the current load of electroplating. Specifically, rather than defined by the film thickness, it is preferably 200 [Omega / cm ² or less in surface resistance, more preferably 25 [Omega] / cm ² or less.

  The conductive film (metal film) obtained as described above has finely dispersed fine particles of electroless plating catalyst and plating metal in the surface graft film by cross-sectional observation by SEM, and further, a relatively large amount of It was confirmed that large particles were precipitated. Since the interface is a hybrid state of the graft polymer and fine particles, the adhesion was good even if the unevenness difference of the interface between the substrate (organic component) and the inorganic substance (electroless plating catalyst or plating metal) was 100 nm or less. .

Next, the “conductive monomer applying step” and the “conductive polymer layer forming step” in the aspect (4) of the conductive material applying step according to the present invention will be described.
In the conductive material attaching step (4), the conductive monomer described below is ionically adsorbed to the interactive group of the graft polymer, particularly preferably to the ionic group, and then is directly used. In this method, a polymerization reaction is caused to form a conductive polymer layer. By this method, a conductive layer made of a conductive polymer is formed.
Here, the conductive layer made of a conductive polymer is formed by polymerizing an interactive group of the graft polymer and an ionically adsorbed conductive monomer, so that it has excellent adhesion to the substrate and durability, and supply of the monomer. By adjusting the polymerization reaction conditions such as the speed, there is an advantage that the film thickness and conductivity can be controlled.

Although there is no restriction | limiting in particular in the method of forming such a conductive polymer layer, From the viewpoint that a uniform thin film can be formed, it is preferable to use the method as described below.
First, the substrate on which the graft polymer is formed is immersed in a solution containing a polymerization catalyst such as potassium persulfate or iron (III) sulfate or a compound having a polymerization initiating ability, and the conductive polymer is stirred while stirring this solution. A monomer that can be formed, such as 3,4-ethylenedioxythiophene, is gradually added dropwise. In this way, the interaction group (ionic group) in the polymerization polymer and the graft polymer imparted with the polymerization initiating ability and the monomer capable of forming the conductive polymer are firmly adsorbed by the interaction, and the monomer The mutual polymerization reaction proceeds, and an extremely thin film of the conductive polymer is formed on the graft polymer on the surface of the insulating resin layer. Thereby, a uniform and thin conductive polymer layer is obtained.

The conductive polymer applicable to this method is 10 ⁻⁶ s · cm ⁻¹ or more, preferably any polymer compound having conductivity of 10 ⁻¹ s · cm ⁻¹ or more. Specifically, for example, substituted and unsubstituted conductive polyaniline, polyparaphenylene, polyparaphenylene vinylene, polythiophene, polyfuran, polypyrrole, polyselenophene, polyisothianaphthene, polyphenylene sulfide, Examples include polyacetylene, polypyridyl vinylene, and polyazine. These may use only 1 type and may use it in combination of 2 or more type according to the objective. Moreover, as long as desired conductivity can be achieved, it can be used as a mixture with other polymers having no conductivity, or a copolymer of these monomers and other monomers without conductivity can be used. be able to.

In the present invention, the conductive monomer itself is strongly adsorbed by forming an interaction with the graft polymer interacting group electrostatically or polarly. Since the polymer layer forms a strong interaction with the graft polymer, even if it is a thin film, it has sufficient strength against rubbing and scratching.
Furthermore, by selecting a material that allows the conductive polymer and the interactive group of the graft polymer to adsorb in the relationship between cation and anion, the interactive group can be adsorbed as the counter anion of the conductive polymer. Therefore, since it functions as a kind of dopant, it is possible to obtain the effect that the conductivity of the conductive polymer layer (conductive expression layer) can be further improved. Specifically, for example, when styrene sulfonic acid is selected as the polymerizable compound having an interactive group, and thiophene is selected as the material of the conductive polymer, the interaction between the graft polymer and the conductive polymer layer results in the interaction between the two. Polythiophene having a sulfonic acid group (sulfo group) exists as a counter anion at the interface, and this functions as a conductive polymer dopant.
Although there is no restriction | limiting in particular in the film thickness of the conductive polymer layer formed in the graft polymer surface, It is preferable that it is the range of 0.01 micrometer-10 micrometers, and it is more preferable that it is the range of 0.1 micrometer-5 micrometers. If the film thickness of the conductive polymer layer is within this range, sufficient conductivity and transparency can be achieved. When the thickness is 0.01 μm or less, there is a concern that the conductivity may be insufficient.

<Electroplating process>
In the aspects (1) to (4) of the conductive pattern forming method of the present invention, after the conductive pattern forming step is performed, a step of performing electroplating (electroplating step) may be included.
In this step, after the formation of the conductive pattern, electroplating can be performed using the metal film (conductive film) formed in this step as an electrode. As a result, a metal film having an arbitrary thickness can be easily formed on the basis of a metal film having excellent adhesion to the insulating resin composition layer. By adding this step, the metal film can be formed in a thickness according to the purpose, and it is suitable for applying the conductive material obtained according to this embodiment to various applications.
As the electroplating method in this embodiment, 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. From the viewpoint of conductivity, copper, gold, and silver are preferable. More preferred.

  The film thickness of the metal film obtained by electroplating differs depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath, the dipping time, or the current density. In addition, the film thickness in the case of using for general electric wiring etc. is preferably 1.0 μm or more, and more preferably 5 μm or more from the viewpoint of conductivity.

  In addition, as described above, the electroplating process in the present invention can be applied to mounting of an IC or the like, for example, by performing electroplating in addition to forming a patterned metal film with a thickness according to the purpose. It can also be done for purposes such as The plating performed for this purpose is selected from the group consisting of nickel, palladium, gold, silver, tin, solder, rhodium, platinum, and compounds thereof on the conductive film or metal pattern surface formed of copper or the like. It can be performed using the material to be used.

In the present invention, when the conductive layer is formed over the entire surface of the insulating film by the above method, the conductive pattern material can be formed by the following method.
The first method is a method in which a resist pattern is formed on a conductive metal film obtained by the present invention and etched to dissolve and remove the conductive metal film in a pattern to form a metal pattern. Called the "law".
The second method is a method in which a resist pattern is formed on the conductive layer obtained by the present invention, and then a metal thin film pattern is formed on the exposed conductive layer portion by conducting conductive metal plating. This is called “semi-additive method”.

"Subtractive method"
The subtractive method is (1) applying a resist layer on the metal film produced by the above method → (2) forming a resist pattern of a conductor to be left by pattern exposure and development → (3) unnecessary metal by etching. Remove film → (4) A method of peeling a resist layer and forming a metal pattern. The film thickness of the metal film used in this embodiment is preferably 3 μm or more, and more preferably in the range of 5 to 20 μm.

(1) Resist layer coating step resist As the photosensitive resist to be used, a photocurable negative resist or a photodissolvable positive resist that dissolves upon exposure can be used. As the photosensitive resist, 1. photosensitive dry film resist (DFR); 2. liquid resist; An ED (electrodeposition) resist can be used. Each of these has its own characteristics. 1. The photosensitive dry film resist (DFR) can be used in a dry manner, so that it is easy to handle. Since the liquid resist can have a thin film thickness as a resist, a pattern with good resolution can be formed. 3. Since an ED (electrodeposition) resist can have a thin film thickness as a resist, a pattern with good resolution can be formed, the follow-up to unevenness of the coated surface is good, and adhesion is excellent. The resist to be used may be appropriately selected in consideration of these characteristics.

Application method 1. Photosensitive dry film The photosensitive dry film generally has a sandwich structure sandwiched between a polyester film and a polyethylene film, and is pressure-bonded with a hot roll while peeling the polyethylene film with a laminator.
The photosensitive dry film resist is described in detail in Japanese Patent Application No. 2005-103677 specification, paragraph Nos. [0192] to [0372] previously proposed by the applicant of the present invention for the formulation, film formation method, and lamination method. These descriptions can also be applied to the present invention.
2. Liquid resist coating methods include spray coating, roll coating, curtain coating, and dip coating. In order to apply both surfaces simultaneously, roll coating and dip coating are preferable because both surfaces can be coated simultaneously.
The liquid resist is described in detail in Japanese Patent Application No. 2005-188722, paragraph Nos. [0199] to [0219] previously proposed by the applicant of the present application, and these descriptions can also be applied to the present invention.

3. ED (Electrodeposition) Resist ED resist is a colloid obtained by suspending photosensitive resist in fine particles and suspending in water. Since the particles are charged, when a voltage is applied to the conductor layer, A resist can be deposited on the conductor layer, and the colloid can be coated on the conductor to form a film.

(2) Pattern exposure process "Exposure"
A base material provided with a resist film on the upper part of the metal film is brought into close contact with a mask film or a dry plate, and exposed to light in a photosensitive region of the resist used. In the case of using a film, the film is exposed with a vacuum printing frame. Regarding the exposure source, a point light source can be used when the pattern width is about 100 μm. When forming a pattern having a pattern width of 100 μm or less, it is preferable to use a parallel light source.
"developing"
Any photo-curing negative resist can be used as long as it can dissolve the unexposed area, or a photo-dissolving positive resist that dissolves upon exposure, so long as it can dissolve the exposed area. An aqueous solution is used. In recent years, an alkaline aqueous solution has been used in order to reduce environmental burden.

(3) Etching process "Etching"
Etching is a process for forming a conductor pattern by chemically dissolving an exposed metal layer without a resist. The etching process is mainly performed by a horizontal conveyor device by spraying an etching solution from above and below. As the etchant, the metal layer is oxidized and dissolved with an oxidizing aqueous solution. Examples of etching solutions include ferric chloride solution, cupric chloride solution, and alkali etchant. Since the resist may be peeled off by alkali, a ferric chloride solution and a cupric chloride solution are mainly used.
In the method of the present invention, since the substrate interface is not roughened, the conductive polymer in the vicinity of the substrate interface has good removability. Since it is bonded to the substrate at the end and has a very high mobility structure, the etching solution can easily diffuse into the graft polymer layer in this etching process, and the interface between the substrate and the metal layer Since the metal component is easily removed from the portion, it is possible to form a pattern with excellent sharpness.

(4) Resist peeling process “Peeling process”
After the metal (conductive) pattern is completed by etching, the etching resist that is no longer needed is no longer needed, and a process of peeling it off is necessary. Peeling can be performed by spraying a stripping solution. The stripping solution varies depending on the type of resist, but generally, a solvent or solution that swells the resist is wiped with a spray, and the resist is swollen and stripped.

"Semi-additive method"
The semi-additive method is: (1) Applying a resist layer on a metal film formed on a graft polymer → (2) Forming a resist pattern of a conductor to be formed by pattern exposure and development → (3) Non-resisting by plating Forming a metal film on the pattern portion → (4) Stripping DFR → (5) A metal pattern forming method of removing an unnecessary metal film by etching. In these steps, the same technique as the “subtractive method” can be used. As the plating method, electroless plating or electroplating described above can be used. Further, the thickness of the metal film to be used is preferably 0.1 to 3 μm in order to complete the etching process in a short time. Further, electrolytic plating and electroless plating may be further performed on the metal pattern formed for the purpose of improving adhesion.

For the metal film formed using the laminate for producing a printed wiring board of the present invention, it is preferable to select a substrate having a surface irregularity of 500 nm or less, but the surface irregularity is more preferably 300 nm or less, still more preferably. Is 100 nm or less, most preferably 50 nm or less. Although there is no restriction | limiting in particular in a lower limit, From the practical viewpoints, such as ease of manufacture, it is thought that it is about 5 nm. In addition, when using the metal film obtained by the present invention as a metal wiring, the smaller the surface unevenness, the smaller the unevenness of the interface between the metal and the organic material forming the metal wiring, and the electrical loss during high-frequency power transmission decreases, preferable. The unevenness of the interface is preferably as small as possible and is preferably 100 nm or less.
From the viewpoint of adhesion, the adhesion between the substrate and the metal film is preferably 0.2 kN / m or more, preferably 0.3 kN / m or more, particularly preferably 0.7 kN / m or more. Here, although there is no upper limit in the numerical value of the said adhesiveness, if it says from a common sense range, it will be about 0.2-2.0 kN / m. The adhesion between the substrate and the metal film in the conventional metal pattern is generally about 0.2 to 3.0 kN / m. Considering this, it can be seen that the metal film obtained from the present invention has practically sufficient adhesion.

The conductive material obtained by the present invention is useful for forming various electrical circuits that require the formation of a fine metal pattern because a highly adhesive metal film is formed on a smooth substrate.
Further, it is particularly useful when a multilayer printed wiring board is produced by repeating a plurality of the above forming methods and laminating build-up layers in multiple stages.
In addition, the laminate for a printed wiring board of the present invention uses a heat-resistant, low-dielectric constant resin such as an epoxy resin, a polyimide resin, a liquid crystalline resin, or a polyarylene resin as a material for the insulating film, thereby roughening the surface of the insulating film. Since it is possible to form a conductive layer that exhibits high adhesion strength and a high-resolution interlayer circuit even if it is not necessary, it is useful for forming a flexible multilayer wiring board.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.
[Example 1]
(Production of substrate)
The base material which has a photosensitive polyimide photosensitive structural material layer on a support body was produced as follows.
[Synthesis Example 1: Synthesis of polyimide precursor compound (P2)]
Under nitrogen, p-hydroxybenzyl alcohol (5.75 g: 46.4 mmol) and triethanolamine (5.16 g: 50.5 mmol) were dissolved in N-methylpyrrolidone (30 ml) and stirred at room temperature for about 30 minutes. did.
Bicyclo (2,2,2) oct-7-ene-2,3,5,6-tetracarboxylic anhydride (5.00 g: 20.2 mmol) was added to this solution and stirred for 5 hours. Subsequently, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (8.28 g: 20.0 mmol) and N-methylpyrrolidone (24 ml) were added and stirred for 1 hour. Further, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate (8.25 g: 21.5 mmol) and N-methylpyrrolidone (10 ml) were added and stirred at 0 ° C. for 3 hours. After that, H ₂ O (5 ml) was added and stirred for 14 hours. The reaction solution was poured into a large amount of MeOH to obtain a polyamic acid (polyimide precursor compound P2) as a white precipitate. The molecular weight (Mw) by GPC was 13,000. Further, the structure was confirmed by ¹ H-NMR and FT-IR.

[Synthesis Example 2: Synthesis of thermally decomposable crosslinking agent (CR1)]
Polyethylene glycol (molecular weight: 2000, manufactured by Wako Pure Chemical Industries, Ltd .: 2.5 mmol) was dissolved in tetrahydrofuran (THF), KOH (250 mmol) was added, and the mixture was heated at 85 ° C. for 2 hours. While maintaining this temperature, chloroethyl vinyl ether (37 mmol) was added dropwise, stirred for 4 hours, and poured into a large amount of n-hexane to obtain a white precipitate. The structure of the following specific compound CR1 was confirmed by ¹ H-NMR and FT-IR.

Formation of low dielectric constant polyamide pattern 100 parts of polyamic acid obtained in Synthesis Example 1, 25 parts of cross-linking agent (CR1) obtained in Synthesis Example 2, 9 parts of diphenyliodonium, 10-dimethoxyanthracene-2-sulfonate 15 A part was dissolved in 400 parts of dimethylformamide to prepare a coating solution for preparing a structural material layer.

  The thus obtained coating solution for preparing a photosensitive structural material layer is applied to a polyethylene terephthalate support, which is a support for application, with a die coater, dried with hot air at 100 ° C. for 5 minutes, and further 170 ° C. And dried for 60 seconds to form a photosensitive structural material layer having a thickness of 30 μm.

(Preparation of a polymer precursor layer film in which a polymer precursor layer is provided on a photosensitive resin structural material layer)
A polymer having an acrylic group as a polymerizable compound and a carboxyl group as an interactive group (hydrophilic having a polymerizable group in the side chain) without performing surface treatment or pretreatment on the surface of the photosensitive structural material layer. The liquid precursor 1 having the following composition containing the functional polymer: P-1 (obtained by the synthesis example described later) was applied with a rod bar # 6 and dried at 100 ° C. for 1 minute to provide a polymer precursor layer. The film thickness of the polymer precursor layer was adjusted to be in the range of 0.2 to 1.5 μm.

(Polymerizable compound-containing liquid composition 1)
・ Hydrophilic polymer (P-1) having a polymerizable group in the side chain 0.25 g
・ Water 5g
・ Acetonitrile 3g

(Synthesis example: Synthesis of polymer P-1 having a double bond)
Polyacrylic acid (average molecular weight 25000, Wako Pure Chemical Industries) 18g was dissolved in DMAc 300g, hydroquinone (Wako Pure Chemical Industries) 0.41g, 2-methacryloyloxyethyl isocyanate 19.4g and dibutyltin dilaurate 0.25g were added. , 65 ° C. for 4 hours. The acid value of the obtained polymer was 7.02 meq / g. The carboxyl group was neutralized with 1N aqueous sodium hydroxide solution, and the polymer was precipitated in addition to ethyl acetate and washed well to obtain hydrophilic polymer P-1.

(Specific Example 1: Formation of an epoxy insulator layer containing an initiator)
20 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) (hereinafter, all compounding amounts are expressed in parts by mass), cresol novolac type epoxy resin (epoxy equivalent 215, Dainippon Ink, Ltd.) 45 parts of Chemical Industry Co., Ltd. Epicron N-673), 30 parts of phenol novolac resin (phenolic hydroxyl group equivalent 105, Phenolite made by Dainippon Ink & Chemicals) 20 parts of ethyl diglycol acetate, 20 parts of solvent naphtha The mixture is heated and dissolved with stirring and cooled to room temperature, and then the phenoxy resin cyclohexanone varnish (YL6747H30 manufactured by Yuka Shell Epoxy Co., Ltd., non-volatile content 30% by mass, weight average molecular weight 47000) composed of Epicoat 828 and bisphenol S. 30 parts and 2-fe Le-4,5-bis (hydroxymethyl) 0.8 parts imidazole, 2 parts of finely divided silica, were added 0.5 parts of silicone antifoaming agent to prepare a epoxy resin varnish.

Furthermore, 10 parts of the polymerization initiating polymer P synthesized by the following method was added to this mixture, stirred and dissolved to prepare an epoxy resin varnish with an initiator. This epoxy resin varnish was coated on the polymer precursor layer of the polymer precursor layer film with a die coater so that the thickness after drying was 7 μm, and dried at 80 ° C. to 120 ° C. to obtain an insulating resin. A composition film was obtained.
Furthermore, a 20 μm polypropylene film is disposed as a protective layer, and a photosensitive component layer, an insulating resin composition layer, and a polymer precursor layer are formed on the support by coating, and the surface is covered with the protective layer. A coated laminate 1 for a printed wiring board of the present invention was obtained.

(Synthesis of polymerization initiating polymer P)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 degrees. [2- (Acryloyloxy) ethyl] (4-benzoylbenzoyl) dimethyl ammonium bromide 8.1g, 2-Hydroxyethylmethacrylate 9.9-g, isopropymethylmethayl 2-methyl-2-azomethylate-2-azomethyl-2'-methyl-2 ) A solution of 0.43 g and MFG 30 g was added dropwise over 2.5 hours. Thereafter, the reaction temperature was raised to 80 ° C., and the reaction was further continued for 2 hours to obtain a polymer P having a polymerization initiating group.

(Specific Example 2: Epoxy insulator layer containing initiator)
5 g of liquid bisphenol A type epoxy resin (epoxy equivalent 176, manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 825), MEK varnish of phenol novolac resin containing triazine structure (manufactured by Dainippon Ink and Chemicals, Phenolite LA-7052, Non-volatile content 62%, non-volatile phenolic hydroxyl group equivalent 120) 2 g, phenoxy resin MEK varnish (manufactured by Tohto Kasei Co., Ltd., YP-50EK35, non-volatile content 35%) 10.7 g, 1- (4- (2-hydroxyethyl) phenyl) -2-hydroxy-2-methylpropan-1-one was mixed with 2.3 g, MEK 5.3 g, and 2-ethyl-4-methylimidazole 0.053 g, and completely dissolved by stirring. A varnish-like epoxy resin composition was prepared. This epoxy resin varnish was coated on the polymer precursor layer of the polymer precursor layer film with a die coater so that the thickness after drying was 90 μm, and dried at 80 ° C. to 120 ° C. to obtain an insulating resin. A composition film was obtained.
Further, a 20 μm polypropylene film is disposed as a protective layer, and an insulating layer and a polymer precursor layer are formed on the support by coating, and the surface thereof is covered with the protective layer. A laminate 2 was obtained.

(Specific Example 3: Epoxy insulator layer containing initiator and polymerizable double bond compound)
70 parts (parts by weight, the same shall apply hereinafter) of phthalic anhydride-modified novolak epoxy acrylate having an acid value of 73 (Nippon Kayaku Co., Ltd., using PCR-1050 (trade name)), acrylonitrile butadiene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd.) , 20 parts of PNR-1H (trade name), 3 parts of alkylphenol resin (made by Hitachi Chemical Co., Ltd., using hitanol 2400 (trade name)), radical photopolymerization initiator (Ciba Geigy, Irgacure 651) 7 parts), 10 parts aluminum hydroxide (made by Showa Denko KK, Heidilite H-42M (trade name) used) and 40 parts methyl ethyl ketone were mixed to prepare an insulating film forming material.
This insulating film forming material resin varnish is applied on the polymer precursor layer of the polymer precursor layer film with a die coater so that the thickness after drying is 50 μm, and dried at 80 ° C. to 120 ° C. Thus, an insulating resin composition film was obtained.
Furthermore, a print of the present invention in which a 20 μm polypropylene film is disposed as a protective layer, an insulating resin composition layer and a polymer precursor layer are formed on a support by coating, and the surface is coated with the protective layer. A laminate 3 for a wiring board was obtained.

(Specific example 4: Phenoxy ether insulator layer containing initiator)
183 g of toluene, 50 g of polyphenylene ether resin (PKN4752, product name manufactured by Nippon GE Plastics Co., Ltd.), 100 g of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10, product name manufactured by Asahi Ciba Co., Ltd.), 9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, trade name, manufactured by Sanko Chemical Co., Ltd.) 28.1 g, manganese naphthenate (Mn content = 6% by weight, Nippon Chemical Industry Co., Ltd.) Co., Ltd.) 0.1% 17% toluene diluted solution, 2,2-bis (4-glycidylphenyl) propane (DER331L, trade name of Dow Chemical Japan Co., Ltd.) 88.3g, (4- (2-hydroxyethyl) phenyl) -2-hydroxy-2-m thylpropan-1-one was added 3.3 g, was adjusted coating liquid was heated and dissolved at 80 ° C.. This insulating film forming material resin coating solution is applied on the polymer precursor layer of the polymer precursor layer film with a die coater so that the thickness after drying is 50 μm, and dried at 80 ° C. to 120 ° C. Thus, an insulating resin composition film was obtained.
Furthermore, a print of the present invention in which a 20 μm polypropylene film is disposed as a protective layer, an insulating resin composition layer and a polymer precursor layer are formed on a support by coating, and the surface is coated with the protective layer. A laminate 4 for a wiring board was obtained.

(Specific Example 5: Polyethersulfone Insulator Layer Containing Initiator)
25% acrylate of cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight 2500) dissolved in diethylene glycol dimethyl ether, 70 parts by weight, polyethersulfone, 30 parts by weight, imidazole-based curing agent (product name 2E4MZ- CN) 4 parts by weight, caprorank tontris (acroyloxy) isocyanurate (Toagosei Co., Ltd., Aronix M325) 10 parts by weight, benzophenone (Tokyo Kasei Co., Ltd.) 5 parts by weight, Michler's ketone (Tokyo Kasei Co., Ltd.) 0.5 parts by weight 20 parts by weight of epoxy resin particles having an average particle diameter of 0.5 μm were mixed. This mixed insulating film forming material resin coating solution is applied on the polymer precursor layer of the polymer precursor layer film with a die coater so that the thickness after drying is 70 μm, and is 80 to 120 ° C. The insulating resin composition film was obtained by drying at ° C.
Furthermore, a print of the present invention in which a 20 μm polypropylene film is disposed as a protective layer, an insulating resin composition layer and a polymer precursor layer are formed on a support by coating, and the surface is coated with the protective layer. A laminate 5 for a wiring board was obtained.

(Preparation of printed wiring board using laminate for printed wiring board)
(1) Application of printed wiring board laminate on substrate Using printed wiring board laminate 1 obtained above, a substrate having a conductive layer in advance to form wiring (patterned glass epoxy) The inner layer circuit board (conductor thickness: 18 μm) is chemically polished, and the printed wiring board laminate 1 is disposed so that the protective layer is peeled off and the substrate and the photosensitive structural material layer are laminated, and a vacuum laminator Was brought into close contact under conditions of 100 ° C. to 110 ° C. at a pressure of 0.2 MPa.
(2) Exposure (formation of graft polymer)
Next, an exposure machine made by Orc is used for the above laminate, and light having a wavelength shorter than 290 nm is cut using a Pyrex (registered trademark) glass filter, and the line width and space width are L / S = 5 μm / 25 μm. The pattern of L / S = 10 μm / 10 μm and a chromium vapor deposition mask pattern having a solid exposure part of 3 cm × 6 cm were overlapped, and pattern exposure was performed for 20 minutes. Thereafter, the obtained film was washed with distilled water to obtain a substrate whose exposed portion was changed to hydrophilic.

(Preparation of printed wiring board using laminate for printed wiring board)
(3) Formation of opening The 365 nm light taken out using the quartz filter for the low pressure mercury lamp was exposed at 500 mJ / cm ² through the quartz glass mask. Then, it heated at 120 degreeC for 4 minute (s) using the hotplate.
Thereafter, development was performed using a developer (a solution in which 20% piperidine of an aqueous solution was added to a 5% KOH aqueous solution), and rinse-dried with pure water. After the development, only the polyimide layer in the exposed part was dissolved and removed to form 100 openings each having a diameter of 50 μm and 100 μm.
Furthermore, the sensitization to the desmear (residue washing) of an opening part and an electroless-plating catalyst was provided by processing at 65 degreeC for 30 minutes using the Melplate Co., Ltd. MLB-496 as a sensitizer.

After the exposure / development treatment, the patterned photosensitive layer was heat-treated at 230 ° C. for 30 minutes using a hot plate. By this heat treatment, the polyamic acid in the photosensitive layer was changed to polyimide by a ring closure reaction. When the cross section of the obtained polyimide was observed with a scanning electron microscope SEM, it was confirmed that a large number of fine pores of several tens of nm were uniformly formed in the patterned photosensitive layer.
When the dielectric constant of the formed pattern was evaluated, it showed a very low dielectric constant of 2.20.

(4) Adhesion of conductive material and its confirmation The substrate of the present invention obtained as described above was formed with a photosensitive on the pattern, and an aqueous solution containing 1.0% by mass of silver nitrate (manufactured by Wako Pure Chemical Industries). After being soaked for 10 minutes, it was washed with distilled water. Thereafter, it is immersed in an electroless plating bath having the following composition for 10 minutes, washed with distilled water, and then electroplated in an electroplating bath having the following composition at a current amount of 3 A / dm ^{2 for} 20 minutes to produce a conductive pattern material. did.
When the opening was observed after electroless plating, copper plating particles were adhered, and it was confirmed that the wall surface of the opening had sensitization to the plating catalyst by the sensitizer treatment described above.
The copper plating particles in the opening cannot be expected to have high conductivity as it is, but after electroplating, the copper film becomes a continuous copper film, and the inner layer circuit and the newly prepared conductive layer in the opening have good conductivity. It was confirmed that it was achieved.
<Electroless plating bath components>
・ 0.3 g of copper sulfate
・ Tartaric acid NaK 1.7g
・ Sodium hydroxide 0.7g
・ Formaldehyde 0.2g
・ Water 48g

<Composition of electroplating bath>
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Copper Greeme PCM (Meltex Co., Ltd.) 3mL
・ Water 500g
[Evaluation]
(Measurement of metal film thickness)
The copper plating thin film on the board | substrate obtained in the Example was cut | disconnected perpendicularly | vertically with respect to the board | substrate plane using the microtome, the cross section was observed by SEM, and the thickness of the formed metal film was measured. The measurement represents an average obtained by measuring three points. As a result of the measurement, the plating thickness was 10 μm.
(Evaluation of unevenness on the substrate interface)
When the copper plating metal thin film on the board | substrate obtained in Example 1 was cut | disconnected perpendicularly | vertically with respect to the board | substrate plane using a microtome, and the cross section was observed by SEM, the unevenness | corrugation of a board | substrate interface can be confirmed. Next, at this substrate interface, three points were taken as random observation points for one sample, and the difference between the maximum peak height and the minimum valley depth at each observation point was set as the unevenness size, and the average value of the three points was obtained. . As a result of measurement, it was found that the unevenness at the substrate interface was 100 nm or less.

(Evaluation of adhesion)
1) After adhering a copper plate (0.1 mm) to the surface of the copper-plated metal thin film of 3 cm × 6 cm on the substrate with an epoxy adhesive (Araldite, manufactured by Ciba Geigy) and drying at 140 ° C. for 4 hours, A 90-degree peeling experiment was conducted based on JISC6481. As a result of the measurement, the peel force was 1.2 kN / m.
2) Moreover, the tape peeling test was done based on JIS D0202-1988 except not cross-cutting in a grid pattern. Using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.), a pattern in which the line width and space width on the conductive pattern material are L / S = 5 μm / 25 μm, and L / S = 10 μm / It peeled, after making it closely_contact | adhere to the part of a 10 micrometer pattern. When 100/100 represents the number of patterns remaining after peeling, 100 samples were prepared, which were 98/100, 1000/100, and 99/100.

(Confirmation of plating of opening)
The shape of the opening was observed by SEM, and the locations where the inner layer circuit and the upper layer circuit were connected by a continuous copper plating film were counted. It was observed that both 100 μm openings and 100 μm openings were covered with a continuous copper plating film.

It was found that all the metal patterns obtained by Example 1 of the present invention had a copper thickness that could sufficiently achieve the conductivity.
Furthermore, all of the metal patterns obtained by the examples of the present invention have excellent surface smoothness with all the irregularities at the film interface being 100 nm or less, and excellent adhesion between the substrate and the metal film. I understood.

(Example 2: Positive photosensitive epoxy resin)
The laminated body 6 for producing a printed wiring board according to the present invention is the same as in Example 1 except that the photosensitive structural material layer of Example 1 is changed to the positive epoxy resin described in Example 1 of JP-T-2004-514173. A similar substrate with a conductive layer was prepared. Copper plating thickness is 10 μm, substrate interface unevenness is 100 nm or less, adhesion is peel force 0.9 N / m, tape peel test result is 97/100, 98/100, 100/100, opening copper plating is 100 100 pieces were coated.
(Example 3: Negative photosensitive epoxy resin)
A laminated body 7 for producing a printed wiring board was produced in the same manner as in Example 1 except that the photosensitive structural material layer of Example 1 was changed to the negative epoxy resin layer of Comparative Example 1 of JP-A-2004-20643.
A substrate was produced in the same manner as in Example 1 or Example 2 except for the exposure for forming the opening. Contrary to Example 1, the exposure for forming the opening using the laminate 7 for producing a printed wiring board of the present invention was performed by exposing a portion to be left with a laser beam of 405 nm. The same exposure machine and developing machine as described in JP-A-2004-20743 were used. When the obtained substrate was evaluated in the same manner as in Example 1, the copper plating thickness was 10 μm, the unevenness at the substrate interface was 100 nm or less, the adhesion was a peel force of 0.8 N / m, and the tape peel test result was 95/100. , 96/100, 99/100, 100 of the copper plating in the opening was coated.

(Example 4: Production of printed wiring board)
In Example 1, instead of using the printed wiring board laminate 1, using the printed wiring board laminates 2 to 5,
Printed wiring boards 2 to 5 were produced and evaluated in the same manner as in Example 1. In any of the printed wiring board laminates, the copper plating thickness is 10 to 11 μm, the unevenness of the substrate interface is 100 nm or less, and the adhesion is a peeling force of 0.8 N / m or more. 95/100 to 98/100, and the number of copper plating films in the opening was 100 out of 100. Thus, each printed wiring board formed using the laminate for producing a printed wiring board according to the present invention has a copper thickness that can sufficiently achieve conductivity, and all the irregularities at the film interface are 100 nm. In the following, it was found that the surface smoothness was excellent, the adhesion between the substrate and the metal film was excellent, and the circuit formation between the multilayer wirings was reliably performed.

Claims (12)

  On the support, a photosensitive resin structural material layer, an insulating resin composition layer capable of generating reactive active species by applying energy, and a polymer compound are formed by reacting with the insulating resin composition layer. And a reactive polymer precursor layer containing an obtainable compound. A laminate for producing a printed wiring board, comprising:   The laminate for producing a printed wiring board according to claim 1, wherein the photosensitive resin structural material layer is an insulating resin that can be patterned by alkali development after exposure.   The laminate for a printed wiring board according to claim 1, wherein the photosensitive resin structural material layer is at least one selected from a photosensitive polyimide resin and a photosensitive epoxy resin.   A printed wiring board laminate according to any one of claims 1 to 3, wherein the photosensitive resin structural material layer is disposed in contact with a substrate surface having a conductive patterned metal film. Then, by exposing from the reactive polymer precursor layer side, a graft polymer is formed in the exposed region, and then the region where the via hole is to be formed is exposed and developed to open the photosensitive resin structural material layer. After the opening is formed, a conductive material is attached to the graft polymer to form a conductive layer in a pattern on the insulating resin composition layer, and the opening is filled with the conductive material. A method for forming a multilayer metal wiring pattern, comprising: connecting a conductive layer on a substrate and a conductive layer formed on an insulating resin composition layer.   The multilayer metal wiring pattern forming method according to claim 4, wherein the opening is filled with a conductive material by metal plating.   5. The method for forming a multilayer metal wiring pattern according to claim 4, wherein the opening is filled with a conductive material by filling the openings with metal fine particles.   The exposure wavelength for generating the graft polymer and the exposure wavelength for forming an opening in the photosensitive resin structural material layer are different from each other. The multilayer metal wiring pattern formation method as described in 2.   8. The multilayer metal wiring pattern forming method according to claim 7, wherein an exposure wavelength for forming an opening in the photosensitive resin structural material layer is longer than an exposure wavelength for generating a graft polymer. .   8. The multilayer metal wiring pattern forming method according to claim 7, wherein an exposure wavelength for forming an opening in the photosensitive resin structural material layer is shorter than an exposure wavelength for generating a graft polymer.   10. The method according to claim 1, wherein an average roughness (Rz) measured by a 10-point average height method on the surface of the insulating resin composition layer is 3 μm or less. A formed metal pattern forming method.   11. A metal thin film formed by the metal pattern forming method according to claim 1, wherein unevenness at an interface with the substrate is 100 nm or less. 11.   A metal thin film formed by the metal pattern forming method according to any one of claims 1 to 10, wherein the metal thin film has an adhesion force with a substrate of 0.5 kN / m or more. .