JP4790380B2 - LAMINATE FOR PRINTED WIRING BOARD AND METHOD FOR PRODUCING PRINTED WIRING BOARD USING SAME - Google Patents

Description

The present invention relates to a laminate for producing a printed wiring board that can be suitably used for producing a printed wiring board, and a method for producing a printed wiring board using the same, and more specifically, a print having high-density wiring used in the field of electronic materials. Printed wiring board laminate that can easily manufacture a wiring board or a copper-clad laminate used for forming the wiring board, a printed wiring board that supports high density mounting, and a printed wiring board that supports mounting The present invention relates to a manufacturing method.

In recent years, along with demands for higher functionality of electronic devices, electronic components have been densely integrated and further mounted with high density. 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 fine wiring, a “subtractive method” is known as a metal pattern forming method useful in the field of conventional conductive patterns, particularly printed wiring boards. In the subtractive method, a metal layer formed on a substrate is provided with a photosensitive layer that is exposed to irradiation with actinic rays, and this photosensitive layer is imagewise exposed and developed to form a resist image. Is a method of forming a metal pattern by etching and finally removing the resist. In the metal substrate used in this method, in order to provide adhesion between the substrate and the metal layer, the substrate interface has been subjected to uneven treatment to develop adhesion by the anchor effect. As a result, the substrate interface portion of the resulting metal pattern becomes uneven, and there is a problem in that the high frequency characteristics deteriorate when used as an electrical wiring. Further, when forming the metal substrate, there is a problem that a complicated process of treating the substrate with a strong acid such as chromic acid is necessary in order to process the substrate.

  In order to solve this problem, a method has been proposed in which a radically polymerizable compound is grafted on the surface of the substrate to modify the surface, thereby minimizing the unevenness of the substrate and simplifying the substrate processing process. However, this method requires an expensive device (γ ray generator, electron beam generator). In addition, since the substrate used is an ordinary commercially available plastic substrate, the graft polymer is not sufficiently generated to attach the electroless plating catalyst or the like firmly there, and the substrate and the conductive layer There was a problem that the adhesion to the surface did not reach the practical strength.

A metal pattern formed on a smooth substrate is useful for a semiconductor device as a wiring (conductive film) of a printed wiring board. In recent years, there has been an increasing demand for electronic devices to process large amounts of data at high speed, and semiconductor devices used for image processing, communication control, etc., have increased internal clock frequency and external clock frequency year by year, and are connected. The number of pins is also increasing. For high-speed conduction, it is important to suppress signal delay and attenuation. To suppress signal propagation delay, it is effective to lower the dielectric constant, and to suppress dielectric loss, it is effective to reduce the dielectric constant and dielectric loss tangent, respectively. Since it is involved as the square root of the dielectric constant, the contribution of the dielectric loss tangent is substantial. For this reason, from the viewpoint of material characteristics, it is advantageous from the viewpoint of speeding up to employ an insulating material having a low dielectric loss tangent characteristic.
In addition, smoothing the surface of the conductor greatly contributes to higher density. In the conventional built-up printed wiring board, the surface roughening treatment is performed in order to ensure the peel strength. However, the present situation is that the unevenness of several microns prevents further fine wiring.
Therefore, from the viewpoint of forming a printed wiring board useful for a semiconductor device, a means for forming a fine and highly adherent metal pattern on a smooth insulating substrate is eagerly desired.

As a method of forming a conductive metal pattern by forming a pattern on a substrate without giving irregularities to the substrate, a method of patterning with photosensitive silicon, applying a catalyst, and then forming a metal pattern by plating (For example, refer to Patent Document 2). However, it cannot be said that the adhesiveness between the silicone resin and the polyimide resin or the epoxy resin that is generally used as an insulating printed wiring board is sufficient, and a method having further excellent adhesiveness is desired.
Accordingly, the applicant of the present application has proposed a method for forming a metal pattern in which metal particles are attached to a fine pattern formed by a graft polymer that is directly bonded to a substrate (see, for example, Patent Document 3). According to this method, a desired fine pattern according to the exposure accuracy can be formed. However, from the practical point of view, the current situation is that further improvement in conductivity is desired by means such as increasing the thickness of the metal layer while maintaining the accuracy of the metal pattern in the line width direction.
JP 58-196238 A JP 2000-349417 A JP 2003-114525 A

An object of the present invention, which has been made in consideration of the above-mentioned conventional technical problems, is to provide a conductive layer having excellent adhesion to the insulating film, small irregularities at the interface with the insulating film, and sufficient thickness. It is an object of the present invention to provide a laminate useful for the production of a printed wiring board that can be easily formed on the solid surface.
Another object of the present invention is to provide a method for producing a printed wiring board having high-definition wiring excellent in adhesion to an insulating film on a substrate using the laminate for printed wiring board of the present invention. It is to provide.

As a result of intensive studies, the inventor has obtained a laminate having a specific insulating resin composition layer, a polymer precursor layer capable of forming a graft polymer, and a reactive polymer composition layer capable of forming a plating resist. Thus, the inventors have found that the above problems can be solved and completed the present invention.
That is, the configuration of the present invention is as follows.
<1> On the support, (B) an insulating resin composition layer containing a photopolymerization initiator, and (A) a polymer compound that reacts with the insulating resin composition layer by the action of the photopolymerization initiator . and reactive polymer precursor layer containing a compound capable of forming a, (C) sequentially and a positive reactive polymer composition layer containing a decomposing compound exposure, the on board (B A laminate for producing a printed wiring board , wherein the laminate is used so that the layers are in contact with each other .
<2> On the support, (B) an insulating resin composition layer containing a photopolymerization initiator, and (A) a polymer compound that reacts with the insulating resin composition layer by the action of the photopolymerization initiator. and reactive polymer precursor layer containing a compound capable of forming a, (C) the positive reactive polymer composition layer and Yusuke that the printed wiring board fabrication laminate containing the decomposed compound exposure Because
On the support, the substrate has the (C) positive-type reactive polymer composition layer, the (A ) reactive polymer precursor layer, and the (B) insulating resin composition layer in sequence. A laminate for producing a printed wiring board, wherein the laminate is used by laminating the laminate.

<3 > A protective film is provided on the surface of the uppermost layer of the laminate for producing a printed wiring board , the support or the protective film is peeled off, and the exposed layer is laminated on a substrate for use <1 > Or <2> The laminate for producing a printed wiring board according to any one of the above.
< 4 > The printed wiring according to any one of <1> to < 3 >, wherein the reactive polymer precursor layer (A) contains a compound having a polymerizable double bond. A laminate for producing a plate.
< 5 > Any one of <1> to < 4 >, wherein the positive reactive polymer composition layer (C) is a plating resist layer containing a photodegradable polymer compound. A laminate for producing a printed wiring board according to 1.

< 6 > An exposure wavelength capable of generating reactive active species in the (B) insulating resin composition layer and a compound decomposed by exposure in the (C) positive reactive polymer composition layer can be decomposed. The exposure wavelength is the same, and by exposure at the wavelength, (B) the formation of a polymer by the reaction between the insulating resin composition layer and (A) the reactive polymer precursor layer, and (C) the positive reaction The laminate for producing a printed wiring board according to any one of <1> to < 5 >, wherein the decomposition in the conductive polymer composition layer occurs and proceeds simultaneously.
< 7 > An exposure wavelength capable of generating reactive active species in the (B) insulating resin composition layer and a compound decomposed by exposure in the (C) positive reactive polymer composition layer can be decomposed. be one and the exposure wavelength are different from each other, firstly, by the exposure of the first wavelength, to decompose the exposed regions in the (C) the positive reactive polymer composition layer, followed by exposure of different wavelengths, ( The polymer compound according to any one of <1> to < 5 >, wherein a polymer compound is produced by a reaction between B) an insulating resin composition layer and (A) a reactive polymer precursor layer. Laminate for producing printed wiring boards.

< 8 > Using the laminate for producing a printed wiring board according to any one of <1> to < 7 >, (B) an insulating resin composition layer and (A) a highly reactive layer on a substrate. A molecular precursor layer; (C) a step of laminating the positive-type reactive polymer composition layer in this order; and (B) a polymer compound that directly binds to the insulating resin composition layer by exposure. Forming a polymer generation region, attaching an electroless plating catalyst or a precursor thereof to the polymer generation region, and forming a circuit pattern by performing electroless plating. A method for producing a printed wiring board.
< 9 > After the step of performing the electroless plating to form a circuit pattern, an unreacted (A) reactive polymer precursor layer, (C) a positive reactive polymer composition layer, and < 8 > The manufacturing method of the printed wiring board as described in the above-mentioned, which has the process of removing.

By using the laminate for producing a printed wiring board of the present invention, a high-definition conductive layer having excellent adhesion with an insulating film and having a sufficient thickness was formed on an arbitrary substrate or insulating film. It can be easily formed on the wiring.
The laminate for a printed wiring board of the present invention is a lamination process in which the laminate is brought into close contact with an arbitrary solid surface such as a substrate, a graft polymer that exposes a region where a conductive layer is to be formed and generates a graft polymer on an insulating film. And a resist patterning step for decomposing the exposed region of the photodegradable resist layer, and further, an electroless plating catalyst precursor is attached to the graft polymer generation region, and then electroplating is performed to conduct the conductive layer A final printed wiring board can be obtained through the conductive layer forming step of forming the layer.
Here, when the exposure wavelength used for forming the graft polymer is the same as the exposure wavelength for decomposing the compound decomposed by exposure in the reactive polymer composition layer, the reactive polymer composition that can be a plating resist. Layer patterning and patterned graft polymer formation can be performed simultaneously.
Further, according to the method of the present invention, the plating resist is not present on the surface of the graft polymer generation region, and the plating resist is present on the non-grafted region of the graft polymer. For this reason, when an electroless plating catalyst or its precursor is adhered to the graft polymer and electroless plating is performed, the formation of the plating film is hindered by the presence of the plating resist in the non-generated region of the graft polymer. The plated film by electroplating is selectively grown only in the thickness direction where there is no resist, and even if the formed conductive film has a sufficient thickness, the growth of the metal film in the lateral direction is hindered. Thus, a high-definition circuit can be formed.
After the formation of the conductive layer, the unreacted polymer composition layer and polymer precursor layer can be removed. The removal can be performed by a known method such as development.

According to the present invention, excellent adhesion to the insulating film, unevenness at the interface with the insulating film is small, and even if the thickness is sufficient, a high-resolution conductive layer can be easily formed on any solid surface. A laminate useful for producing a printed wiring board can be provided.
Moreover, by using the laminate for a printed wiring board of the present invention, a method for producing a printed wiring board having a high-definition wiring excellent in adhesion to an insulating film on a substrate can be provided.
The printed wiring board obtained by the present invention has a fine wiring pattern excellent in high-frequency characteristics, and can be suitably used for a multilayer wiring board.

The laminate for a printed wiring board according to the present invention comprises a support for holding the laminate, and a polymer (A) reactive polymer capable of producing a polymer compound (graft polymer) at least by applying energy such as exposure. It has three layers: a precursor layer, (B) an insulating resin composition layer capable of generating a graft polymer on the surface, and (C) a photodegradable reactive polymer composition layer capable of forming a plating resist. It is characterized by.
In the present specification, “(A) reactive polymer precursor layer” is referred to as “(A) layer” or “polymer precursor layer”, and “(B) insulating resin composition layer” is referred to as “( "B) layer" or "insulating film" and "(C) reactive polymer composition layer containing a compound that decomposes upon exposure" are referred to as "(C) layer" or "photodegradable layer", respectively. There is.
In addition, in order to protect various functions of the laminate including the support and the (A) layer, the (B) layer, and the (C) layer formed thereon until use, the surface of the laminate is provided. It is preferable to provide a protective layer.
The order of formation of these (A) reactive polymer precursor layer, (B) insulating resin composition layer, and (C) reactive polymer composition layer containing a compound that decomposes upon exposure is arbitrary. For example, even if the (B) layer, the (A) layer, and the (C) layer are sequentially provided on the support, the (C) layer is first provided on the support, and ( A layer and (B) layer may be sequentially provided.
In the present invention, “sequentially” means that these layers exist 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 useful for formation of the printed wiring board of this invention is demonstrated one by one.

[(A) Reactive polymer precursor layer]
The reactive polymer precursor layer includes at least one polymer precursor, that is, a compound that can form a polymer compound by reacting with the insulating resin composition layer by the action of a photopolymerization initiator described later. contains. The polymer precursor here refers to 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. It refers to compounds that can improve adhesion. Such a polymerizable compound or a compound capable of crosslinking structure may further have a functional group capable of interacting with a conductive material which is a partial structure to which a conductive material can be attached as described later. Such a compound further having a functional functional group is also included in the polymer precursor. Since the polymer compound produced by the reaction of these polymer precursors (hereinafter appropriately referred to as a graft polymer) is one that adheres an electroless plating catalyst or the like, the polymer precursor is A partial structure that can form a polymerization reaction or a crosslinked structure and is necessary for bonding to the insulating resin composition layer, such as “unsaturated double bond capable of radical polymerization”, and an electroless plating catalyst described later It is preferable to use a compound having both of “functional groups capable of interacting with an electroless plating catalyst or the like” necessary for adhering a polymer to a graft polymer.

(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.
In addition, as another embodiment of the polymer precursor, an oligomer or polymer compound having a reactive active group in the molecule, for example, a reactive active group represented by an epoxy group, an isocyanate group, or an azo group Or the combination of a crosslinking agent and a crosslinkable compound etc. are mentioned.

The polymer precursor further needs to have a functional group capable of interacting with an electroless plating catalyst described later or an electroless plating catalyst that is a partial structure to which the precursor can be attached.
The functional group capable of interacting with the electroless plating catalyst 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 other functional groups having affinity with the electroless plating catalyst include hydrophilic groups.

  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 an unsaturated double bond and having a functional group capable of interacting with an electroless plating catalyst or the like 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, it has an unsaturated double bond capable of radical polymerization (hereinafter appropriately referred to as a polymerizable unsaturated group) and has a functional group capable of interacting with an electroless plating catalyst. From the viewpoint of ease of adhesion and adsorption of these compounds and removal of unreacted substances after the graft reaction, the compound has a hydrophilic group that is a polar group, a hydrophilic polymer, a hydrophilic macromer, Hydrophilic monomers are preferred.

-Hydrophilic monomer-
Specific examples of the hydrophilic monomer that can be used in the present invention include the following monomers.
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 carboxyl 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 as follows. As a synthesis method, (a) a method of copolymerizing a hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group, (b) copolymerizing a hydrophilic monomer and a monomer having a double bond precursor, Next, a method of introducing a double bond by treatment with a base or the like, and (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group. Among these, from the viewpoint of synthesis suitability, (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group is particularly preferable.
In the methods (a) and (b), the hydrophilic monomer used for the synthesis of the radical polymerizable group-containing hydrophilic polymer includes (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali. Metal salt and amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, 3-vinylpropion Acid or alkali metal salt and amine salt thereof, vinyl sulfonic acid or alkali metal salt and amine salt thereof, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfone Monomers having hydrophilic groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups or salts thereof, hydroxyl groups, amide groups and ether groups, such as acid phosphooxypolyoxyethylene glycol mono (meth) acrylate Can be mentioned.
As the hydrophilic polymer used in the method (c), a hydrophilic homopolymer or copolymer obtained using at least one selected from these hydrophilic monomers is used.

  When the radically polymerizable group-containing hydrophilic polymer is synthesized by the method (a), examples of the monomer having an ethylene addition polymerizable unsaturated group that is copolymerized with the hydrophilic monomer include an allyl group-containing monomer. Examples include allyl (meth) acrylate and 2-allyloxyethyl methacrylate. Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (b), a monomer having a double bond precursor that is copolymerized with a hydrophilic monomer is 2- (3-chloro-1-oxopropoxy). ) Ethyl methacrylate. Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (c), a reaction between a carboxyl group, an amino group or a salt thereof in the hydrophilic polymer and a functional group such as a hydroxyl group and an epoxy group is performed. It is preferable to introduce an unsaturated group using it. Examples of the monomer having an addition polymerizable unsaturated group used for this purpose include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

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 can be easily formed on the support or on the (B) insulating resin composition layer described later by applying and drying the coating. Can do.
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.

Therefore, when a macromonomer or polymer is used as the polymer precursor, the (A) reactive polymer precursor layer having a uniform film thickness can be easily formed. As a result, a uniform graft polymer is obtained. It can be seen that a generation 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 total solid content constituting the layer (A), and more preferably in the range of 30 to 100% by mass. preferable.

(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 to form the polymer precursor layer (A) together with the radical polymerizable group-containing hydrophilic compound, and is useful for improving film properties. 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. . 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 is preferably a water-soluble oligomer or polymer having a molecular weight of 500 or more.
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 are (A) improved coating surface properties when forming a film of the reactive polymer precursor layer, or providing the film with flexibility and generating cracks when folded in the film state. Used for suppression. As the plasticizer, surfactant, and viscosity modifier, known materials that are generally used are used.

(Formation of reactive polymer precursor layer)
(A) The reactive polymer precursor layer is obtained by applying and drying a coating solution prepared by dissolving the above-described components in an appropriate solvent on a support or on an insulating film (B) described later. Is formed.
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.

(A) 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 0.2 to 5 μm. Within this range, the thickness of the graft polymer layer formed thereafter is in a suitable range, and excellent adhesion can be ensured even when an electroless plating catalyst or the like is attached in the subsequent steps.
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 0.1 μm to 0.7 μm. Therefore, the thickness of the polymer precursor layer is set to 10 μm. Even if it is too thick, not only will the material be involved in graft polymer formation, which will lead to increased costs, but it will also be difficult for the exposure light source to reach the depths, making it difficult to remove unnecessary graft polymer precursor materials. It brings many problems such as becoming.

[(B) Insulating Resin Composition Layer Containing Photopolymerization Initiator ]
For 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, build-up substrate, or flexible substrate can be used. These resins are made of a thermosetting resin, a thermoplastic resin, or a resin mixture thereof. These resins are in the present invention, from the viewpoint of causing easily grafting reaction between formed is (A) reactive polymer precursor layer in the vicinity, and a photopolymerization initiator in these insulating resins Ru using things. Further, a polyfunctional acrylate monomer may be added for the purpose of increasing the graft reactivity or the strength of the insulator 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 the electrical characteristics. In addition, the “insulating resin” in the present invention means a resin having an insulating property to the extent that it can be used for a known insulating film. 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 thermosetting resins 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 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 comprises (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.

(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 -Polyfunctional amino compounds such as triaminotriazine can be mentioned.
The resin composition of the present invention may contain an epoxy resin curing agent. For example, polyfunctional phenols, amine louis, imidazole compounds, acid anhydrides, organic phosphorus compounds, and halides thereof may be used, but those that do not inhibit the 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. Typical 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 of these 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, methacrylic acid or acrylic acid is used for a thermosetting resin or a thermoplastic resin, for example, an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, A resin obtained by subjecting a part of the resin to a (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 photopolymerization initiator added to the insulating resin composition layer)
The (B) insulating resin composition layer of the present invention contains a photopolymerization initiator. The photopolymerization initiator (B) Ru earthenware pots used for the insulating resin composition layer of the present invention may be a small molecule, it may be a polymer, generally known 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. Usually, sulfonium salts and iodonium salts used as photoacid generators also act as radical generators upon irradiation with light, and these may be used in the present invention. Further, for the purpose of increasing sensitivity, a sensitizer may be used in addition to the radical photopolymerization initiator. 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 photopolymerization initiator to be contained in the insulating resin is selected depending on the application of the surface graft material to be used, in general, about 0.1 to 50% by weight in terms of solid content in the insulator layer It is preferable that it is about 1.0-30.0 mass%.

(Other additives contained in the insulating resin composition layer)
In the layer (B) of the present invention, a composite (composite) of a resin and other components is used to enhance the mechanical strength, heat resistance, weather resistance, flame resistance, water resistance, electrical characteristics, 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 peculiar to the resin are reduced. The graft polymerization reaction also does not proceed.

(Insulating resin composition layer shape)
The thickness of the (B) insulating film in the present invention is generally in the range of 1 μm to 200 μm, and preferably in the range of 10 μm to 150 μm.
From the viewpoint of improving the physical properties of the formed conductive layer, 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 material, 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 extremely 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) The layer supports the coating solution prepared so as to improve the coating property by dissolving the above-described components in an appropriate solvent or varnishing. A film for forming an insulating film is formed on the body or by applying and drying the polymer precursor layer (A) described above. By forming a film for forming an insulating film into a film, the thickness accuracy is high, handling properties, alignment accuracy, and the like are improved, and the film can be suitably used as an insulating film for various electronic parts, an adhesive film, 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 those 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 liquid 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. It 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. All of the various blending components may be added simultaneously, the order of addition may be set as appropriate, and if necessary, some blending components may be added after preliminary kneading in advance. .

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 carried out 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 it is more preferable to evaporate by heating with ventilation. For example, by coating on one side of the support described below, and heating and drying at 80 ° C. to 200 ° C. for 0.5 to 10 minutes to remove the solvent, the film is in a semi-cured and non-sticky state It is preferable to do.

[(C) Positive Reactive Polymer Composition Layer Containing Compound that Decomposes upon Exposure]
The layer (C) contains a photodegradable polymer compound and is a layer from which the region is removed by exposure, and is useful as a positive type plating resist layer.
The layer (C) is a photoacid generator that is easily decomposed by light irradiation to generate an acid, and an acid-decomposable group that is an alkali-insoluble or hardly-soluble resin, and is generated from the photoacid generator. The acid-decomposable group is decomposed by the action of the acid to form a layer comprising a photosensitive composition containing a resin that becomes alkali-soluble, or a photoacid generator, an alkali-soluble resin, and the alkali-soluble resin. Photosensitivity containing a compound having an action of inhibiting alkali solubility and having an action of reducing or eliminating the ability to inhibit alkali solubility by the action of an acid or promoting alkali solubility of the alkali-soluble resin. A layer made of the composition is preferred.

(Photoacid generator)
As the photoacid generator that can be used in the layer (C) in the present invention, known photoacid generators can be mentioned without limitation.
For example, diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TSBal etal, Polymer, 21, 423 (1980), U.S. Pat. -140140 ammonium salt, DCNecker etal, Macromolecules, 17, 2468 (1984), CS Wen etal, Teh, Proc. Conf. Rad. Curing ASIA, p. 478 Tokyo, Oct (1988), U.S. Patent No. Phosphonium salts described in 4,069,055, 4,069,056, etc., JV Crivello etal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150848, JP-A-2-965514, etc., JV Crivello etal, Polymer J. 17, 73 (1985), JV Crivello etal. J. Org. Chem., 43, 3055 (1978), WR Wattetal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Crivelloetal, Polymer Bull., 14, 279 (1985), JV Crivello etal, Macromorecules, 14 (5), 1141 (1981), JV Crivello etal, J. Polymer Sci., Pol ymer Chem. Ed., 17, 2877 (1979), European Patent 370,693, US Patent 3,902,114, European Patents 233,567, 297,443, 297,442, US Patents 4,933,377, 410,201, 339,049 No. 4,760,013, No. 4,734,444, No. 2,833,827, Korean Patent No. 2,904,626, No. 3,604,580, No. 3,604,581, etc.,

Selenonium salts described in JV Crivello etal, Macromorecules, 10 (6), 1307 (1977), JV Crivelloetal, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), CS Wen etal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281 JP 55-32070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63 Organohalogen compounds described in JP-A-70243, JP-A-63-298339, etc., K. Meier etal, J. Rad. Curing, 13 (4), 26 (1986), TP Gill etal, Inorg. Chem., 19 , 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), JP-A-2-16145, and the like,

S. Hayase etal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis etal, J. PholymerSci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahedron Lett., (24), 2205 (1973), DHR Barton etal, J. Chem Soc., 3571 (1965), PM Collins etal, J. Chem. SoC., Perkin I, 1695 (1975), M. Rudinstein etal, Tetrahedron Lett., (17), 1445 (1975), JW Walker etal J. Am. Chem. Soc., 110, 7170 (1988), SCBusman etal, J. Imaging Technol., 11 (4), 191 (1985), HMHoulihan etal, Macormolecules, 21, 2001 (1988), PMCollinsetal, J. Chem. Soc., Chem. Commun., 532 ( 1972), S. Hayasetal, Macromolecules, 18, 1799 (1985), E. Reichmanis etal, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan etal, Macromolcules, 21, 2001 ( 1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, JP-A-53- O-Nitrobenzyl described in No. 133022, etc. A photoacid generator having a type protecting group,

M. TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Berner etal, J. Rad. Curing, 13 (4), WJ Mijs etal, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi etal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, U.S. Patent Nos. 4,618,564, 4,371,605 4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-140109, etc., and compounds that generate sulfonic acid by photolysis, such as iminosulfonate And disulfone compounds described in JP-A-61-166544.

  As content in the reactive polymer composition layer of the photoacid generator which decomposes | disassembles by said exposure and generate | occur | produces an acid, it is 0.001-40 mass% normally in conversion of solid content, Preferably 0.01 -20% by mass, more preferably 0.1-5% by mass.

  In the present invention, since the photodegradable layer is a layer composed of a positive photosensitive composition, examples of the alkali-soluble binder used in the (C) layer include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol- In addition to cresol / formaldehyde co-condensation resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, N- (4-hydroxyphenyl) methacrylamide copolymer, hydroquinone monomethacrylate copolymer, Examples thereof include a sulfonylimide polymer described in Japanese Patent No. 28244, and a carboxyl group-containing polymer described in Japanese Patent Laid-Open No. 7-36184. In addition, an acrylic resin containing a phenolic hydroxyl group described in JP-A No. 51-34711, an acrylic resin having a sulfonamide group described in JP-A No. 2-866, a urethane resin, etc. Alkali-soluble polymer compounds can also be used. These alkali-soluble binders may be used singly or in combination of two or more.

In addition, a resin in which an alkali-soluble group is protected with an acid-decomposable group can be used in combination with the photoacid generator. This resin is a compound having a —C—O—C— or —C—O—Si— bond, and examples thereof include the following compounds.
(A) including those selected from the group consisting of at least one orthocarboxylic acid ester and carboxylic acid amide acetal, the compound of which can have polymerizability, the above group as a bridging element in the main chain or on the side A compound which can occur as a side substituent,
(B) an oligomeric compound or a polymer compound containing in the main chain a compound selected from the group of repeating acetals and ketals;
(C) a compound comprising at least one enol ester or N-acylamino carbonate group,
(D) β-ketoester or β-ketoamide cyclic acetal or ketal,

(E) a compound containing a silyl ether group,
(F) a compound containing a silyl enol ether group,
(G) a monoacetal or monoketal in which the aldehyde or ketone component has a solubility of 0.1 to 100 g / liter with respect to the developer;
(H) tertiary alcohol ethers, and
(I) Carboxylic acid esters and carbonates of tertiary allylic or benzylic alcohols.

The compounds (a) that can be cleaved by the above acids are described in German Patent Publication Nos. 2,610,842 and 2,928,636. Mixtures containing the compound (b) are described in German Patents 2,306,248 and 2,718,254. The compound (c) is described in European Patent Publication Nos. 0,006,626 and 0,006,627. The compound (d) is described in European Patent Publication No. 0,202,196, and the compound used as (e) is described in German Patent Publication Nos. 3,544,165 and 3,601. , 264. The compound (f) is described in German Patent Publication Nos. 3,730,785 and 3,730,783, and the compound (g) is described in German Patent Publication No. 3,730,783. In the issue. The compound (h) is described in, for example, US Pat. No. 4,603,101, and the compound (i) is described in, for example, US Pat. No. 4,491,628 and JM Frechet et al. ImagingSci. 30, 59-64 (1986)).
The content of the compound protected with these acid-decomposable groups in the (C) layer is usually 1 to 60% by mass, more preferably 5 to 40% by mass, based on the total solid content of the composition. is there.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, acrylic resins, polyhydroxystyrene resins More preferred are resins and polysiloxane resins. Further, from the viewpoint of developing property control, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable.

  In particular, acrylic resins (binders that may contain a polymerizable group) are preferable. Examples of the acrylic resins include benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like. Copolymers comprising monomers selected from: Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB), and Dial NR series (Mitsubishi Rayon) Manufactured by Co., Ltd.), Biscoat R264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like are preferable.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ ×. 10 ⁴ polymers are particularly preferred.
Moreover, as content in the (C) layer of an alkali-soluble binder, 10-90 mass% is preferable with respect to the total solid of this composition, 20-80 mass% is more preferable, 30-70 mass% is especially preferable. preferable.

The layer (C) is suitable for the purpose of improving the alkali solubility or adjusting the glass transition temperature of the composition to prevent the film from becoming brittle or heat resistance from being deteriorated. Molecular compounds may be added. Examples of the alkali-soluble low-molecular compound include dialkylsulfonamide compounds, dialkylsulfonylimide (—SO ₂ —NH—CO—) compounds, and dialkyl disulfonylimide (—SO ₂ —NH—SO ₂ —) compounds. Mention may be made of compounds containing acidic groups. The content of the alkali-soluble low molecular compound is preferably 40% by weight or less, more preferably 30% by weight or less, based on the resin having a substituent that increases the solubility in an alkali developer by the acid. More preferably, it is 25 weight% or less.

(C) Formation of the layer (C) In order to form the layer, it is possible to apply all standard components by dissolving them in a suitable solvent. In addition, the reactive polymer composition layer is formed into a film in advance. It is also possible to form a film and laminate it.
(C) A preferable solvent used for forming the layer is a coating film in which the above-mentioned polymer compound and the component comprising the photoacid generator of the present invention are sufficiently dissolved, and the solution is uniform by a method such as spin coating. Any solvent may be used as long as it is an organic solvent capable of forming. Moreover, you may use individually or in mixture of 2 or more types.
Specifically, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tertiary butyl alcohol, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 2-methoxybutyl acetate, 2-Ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidinone, cyclohexanone, cyclopentanone, cyclohexanol, methyl ethyl ketone, 1,4 -Dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoiso Ropirueteru, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and the like, but the present invention is of course not limited thereto.

The basic components of the layer (C) in the present invention are the photoacid generator, the polymer compound, and a solvent (optionally an alkali-soluble low-molecular compound), but if necessary, a surfactant, You may add other components, such as a pigment | dye, a stabilizer, a coating property improving agent, and dye.
Whether the layer (C) is formed by a coating method or a laminate method, the thickness is preferably 5 to 50 μm, more preferably 10 to 40 μm.

(C) A plating resist is formed by exposing and developing the layer.
As the exposure means, any exposure means such as ArF excimer laser stepper exposure as long as the exposure wavelength is included in the range of 150 nm to 450 nm may be applied. Particularly preferable exposure means include KrF excimer laser, ArF. Stepper-exposure exposure means such as excimer laser, UV generator such as low-pressure mercury lamp and high-pressure mercury lamp, fluorescent lamp, laser, LED, etc. Is mentioned.
By setting the exposure wavelength to the same range as the graft polymer formation wavelength of the layer (B), the formation of a patterned plating resist and the formation of a patterned graft polymer capable of attaching a plating catalyst or the like are performed simultaneously. Can do.

Further, as a developer for developing the exposed area of the layer (C) after exposure and forming a resist pattern, an appropriate organic solvent according to the solubility of the polymer compound used, or a mixed solvent thereof, or What is necessary is just to select suitably from the alkali solution of moderate density | concentration, aqueous solution, or its mixture, or the mixture of an alkali solution, a suitable organic compound, and an organic solvent.
Examples of the organic solvent and organic compound used include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2,6-dimethylcyclohexanone, and 3-methyl-2-cyclopentanone, methyl alcohol , Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 3,5-dimethylcyclo Alcohols such as hexanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, etc., tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, vinegar Isoamyl, benzene, toluene, xylene, phenol, acetonitrile, and an organic solvent such as dimethylformamide. Examples of the alkaline solution used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, and ammonia, and organic solvents such as ethylamine, propylamine, diethylamine, dipropylamine, trimethylamine, and triethylamine. An aqueous solution containing an amine and an organic ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, tolethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, or an organic solvent, And mixtures thereof, but are not limited to these.

[Support]
The laminate for a printed wiring board of the present invention has at least the (A) layer, the (B) layer, and the (C) layer between a support serving as a base film and a protective layer that will be described later provided as desired. It becomes. The support is used as a base of the laminate until the laminate of the present invention is brought into contact with a predetermined substrate or the like and used for forming a printed wiring board.
The base film that can be used for the support includes polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate, resin sheets such as polyamide, polyimide, and polycarbonate, and processed paper with controlled surface adhesion, such as release paper. Metal foils such as copper foil and aluminum foil.

The thickness of the support is generally 2 to 200 μm, more preferably 5 to 50 μm, still more preferably 10 to 30 μm. If the sheet used as the support is too thick, there is a problem in handling properties when the laminate is actually formed using the laminate, particularly when the laminate is laminated on a predetermined substrate or wiring. May come out.
In addition, the sheet surface constituting the support may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
By making the width of the support about 5 mm longer than the width of the insulating film or polymer precursor layer, it is possible to prevent adhesion of the resin in the laminate when laminating with other layers, Advantages such as easy peeling of the support base film during use can be obtained.

[Adhesive layer, cushion layer]
When forming the laminate for a printed wiring board of the present invention, in order to improve the adhesion with other layers formed adjacent to the support, or to improve the cushioning during lamination, the adhesion In order to improve, after applying a resin varnish dissolved in a predetermined organic solvent on the surface of the base film serving as a support, the solvent is dried by heating and / or hot air blowing to form a room temperature solid resin composition, and an adhesive layer Alternatively, a cushion layer can be produced.
Here, the organic solvent used for application of the resin varnish is usually a solvent, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate. Esters, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. It can be used in combination of more than one species.

[Protective layer]
As the resin film for forming the protective layer, the same material as that used for the support may be used, or a different material may be used. As well as the support, the surface adhesiveness is controlled, such as polyolefins such as polyethylene, polyvinyl chloride, and polypropylene, polyesters such as polyethylene terephthalate, polyamide, polycarbonate, and other resin sheets, and release paper. Processed paper, 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, and 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 release treatment in addition to the mat treatment and embossing.

  The laminate for a printed wiring board of the present invention obtained by laminating these layers is further laminated with this protective film, for example, wound into a roll and stored.

[Method for producing laminate for printed wiring board]
As a method for producing a laminate for a printed wiring board of the present invention, first, (B) an insulating resin composition layer containing a polymerization initiator in an insulating resin is provided on the support, and then ( A) forming a polymer precursor layer, and further forming (C) a reactive polymer composition layer containing a photodegradable compound, and (C) covering the photodegradable layer with a protective layer, Alternatively, (C) a photodegradable layer is formed on a support, then (A) a polymer precursor layer is formed, and (B) an insulating film is formed, and (B) the surface of the layer Is coated with a protective layer. Further, an adhesive layer may be provided between the support and (A) the polymer precursor layer, or between (A) the polymer precursor layer and (B) the insulating film.
Thus, the laminated body for printed wiring boards of this invention is obtained.

  In the laminate of the present invention, on the surface of the support, an insulating resin such as an epoxy resin, a polyimide resin, a liquid crystalline resin, or a polyarylene resin is contained in a polymerization initiator to provide an initiator-containing insulator layer. A major feature is that a polymer precursor layer is provided adjacent to it, and by applying this laminate to the surface of an arbitrary substrate or wiring, and applying energy, it is desired. Insulator layers having the above characteristics and a graft polymer generation region directly bonded to the surface of the insulator layer can be formed. Since this graft polymer has excellent affinity with the electroless plating catalyst or its precursor, it has excellent adhesion of the formed electroless plating film. By using the laminate for a printed wiring board of the present invention, it is smooth and uniform. Such a conductive film can be formed in a desired region in accordance with energy application.

In the present invention, by including a polymerization initiator in the insulating resin, the adhesion between the insulator layer and the graft 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 the surface graft, which increases the interaction with the electroless plating catalyst layer, resulting in improved adhesion. Can be considered.
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 printed wiring board using laminate for printed wiring board]
Next, the manufacturing method of the multilayer printed wiring board using the laminated body for printed wiring boards of this invention is demonstrated, referring drawings.
1A to 1F are schematic cross-sectional views showing a process of forming a conductive layer in a pattern on the surface of a desired internal circuit board using the laminate for a printed wiring board of the present invention.
FIG. 1A shows a laminate 10 of the present invention. In this laminate 10, (C) a photodegradable layer 14 is formed on the surface of a support 12, then (A) a polymer precursor layer 16 is formed, and (B) an insulating film 18 is further formed. And has a protective layer 20 on its surface. When laminating the laminate 10 to the patterned inner layer circuit board 22, as shown in FIG. 1B, the protective film 20 is removed and then turned over to invert the insulating resin composition layer 18 to the inner circuit board. As shown in FIG. 1 (C), the two are brought into close contact with each other, and the room temperature solid photodegradable layer 14, the polymer precursor layer 16, the insulating resin composition from the support (base film) 12 side. The laminate of the material layer (insulating film) 18 is laminated while being pressurized and heated. Here, although not shown, by laminating under the condition that the resin flow at the time of laminating is not less than the conductor thickness of the inner layer circuit and half or more of the through hole depth of the inner layer circuit and / or the surface via hole depth, The coating of the inner layer circuit pattern and the resin filling in the through hole and / or the surface via hole can be performed simultaneously.

Thereafter, the support 12 is peeled off, or in the case of the support 12 that can transmit an exposure light source for applying energy, as shown in FIG. Thus, in the exposure region, (A) the polymerizable compound in the polymer precursor layer 16 has a strong chemistry at the insulating film / precursor layer interface, based on the active point generated from the initiator in (B) the insulating film 18. Bonding occurs and a graft polymer 24 is formed. In the (C) photodegradable layer 14, the (C) layer 14 component in the exposed region is photodegraded, and the solubility of the layer is remarkably improved.
Thereafter, by removing the unreacted (A) polymer precursor layer and (C) photodegradable layer, as shown in FIG. (E), only the region where (C) layer 14 is decomposed and removed is grafted. Since the polymer 24 is generated, the electroless plating catalyst 26 is attached thereto, and then electroless plating is performed, so that the plating film 28 is formed on the plating resist [(C) layer] 14 in the graft polymer 24 generation region. Since the plating resist [(C) layer] 14 is removed in order to selectively grow in the non-existing region, a printed wiring board having a high-definition and sufficient thickness wiring 28 as shown in FIG. A laminate having a conductive layer 28 for forming a printed wiring board can be obtained.

(Granting energy)
In the present invention, the formation of the graft polymer and the decomposition of the layer (C) are performed by irradiation with radiation such as heat or light. Heating is performed using a heater or infrared rays. 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.
As the wavelength of the light used for the generation of the polymer of the (A) layer and the decomposition of the (C) layer, any wavelength may be used in the same case, but a wavelength of 150 nm to 450 nm is preferably used. Is preferred. If a longer wavelength is used, fine line reproducibility may be deteriorated. Moreover, when the production | generation of the polymer of (A) layer and the decomposition wavelength of (C) layer differ, it is preferable to use the wavelength of the same 150 nm-450 nm area | region, However, depending on the direction of the decomposition wavelength of (C) layer The use of a short wavelength region is preferable from the viewpoint of fine line reproducibility. In this case, it is preferable that the polymer generation wavelength of the (A) layer is transmitted by the decomposition of the (C) layer.
The photodissolvable positive resist that dissolves upon exposure is developed with a solvent that can dissolve the exposed portion. Although there is no restriction | limiting in particular in the solvent used here, the organic solvent and alkaline aqueous solution are mainly used, and alkaline aqueous solution is used in recent years from environmental load reduction.

  High adhesion between the insulating film and the electroless plating catalyst is as follows. 1. Strong and high-density bond between the insulating film and the graft polymer; The produced graft polymer and the electroless plating catalyst are exhibited 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 electroless plating catalyst in addition to adding a polymerization initiator to the insulating film.

Hereinafter, a typical method for attaching an electroless plating catalyst or the like to the graft polymer and then forming a conductive layer will be described.
In the present invention, an electroless plating catalyst or a precursor thereof is applied to the graft polymer formed on the surface of the insulating film, and the electroless plating is performed to form a conductive layer in a pattern, but the conductivity is further increased. Therefore, a method such as electroplating may be added.

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 interacting with the electroless plating catalyst or precursor thereof is generated, and the graft After applying an electroless plating catalyst or a precursor thereof to the polymer, a method of forming a metal thin film by performing electroless plating is employed. 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 strength as well as conductivity. And show 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, since the non-grafted region of the graft polymer is covered with the (C) layer having a plating resist function, the conductive film formed by electroless plating or subsequent electroplating is plated. Since it grows selectively only in a region where no resist exists, a high-resolution conductive film is formed even if the thickness is sufficient.

  In the present invention, the graft polymer has an interactive group that interacts with the electroless plating catalyst or a precursor thereof, and a step of applying the electroless plating catalyst or the precursor thereto (application of an electroless plating catalyst or the like) A conductive film is formed by sequentially performing a step) and a step of performing electroless plating to form a metal thin film (electroless plating step). That is, a graft polymer having a functional group (that is, a polar group) that interacts with an electroless plating catalyst or a precursor thereof interacts with the electroless plating catalyst or a precursor thereof, and then undergoes an electroless plating treatment to perform metal A thin film 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.
Hereinafter, this process will be described in detail.

<Application process for electroless plating catalyst>
In this step, an electroless plating catalyst or a precursor thereof is applied 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 having the charge adjusted in this way can interact with the interactive group (polar group) of the graft polymer. By making it act, a metal colloid (electroless plating catalyst) can be made to adhere to a graft polymer.

[Electroless plating catalyst precursor]
The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion that is the electroless plating catalyst precursor is applied to the substrate in the step (b), and before being immersed in the electroless plating bath, the metal ion is separately changed to a zero-valent metal by a reduction reaction as an electroless plating catalyst. 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, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.

  As a method 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 the dissociated metal ions is prepared, and the solution is applied to the surface of the glass substrate where the graft polymer is present, or the insulating resin composition layer having the graft polymer is immersed in the solution. . 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%. Further, the contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour.

<Electroless plating process>
In this step, the conductive film (metal film) is formed by performing electroless plating on the insulating resin composition layer to which the electroless plating catalyst or the like is applied from the electroless plating catalyst or the like applying step. The That is, by performing electroless plating in this step, a high-density conductive film (metal film) is formed on the graft polymer obtained by 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.
Further, 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, it is preferably 0.5 μm or more, and more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

  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. .

<Electroplating process>
After performing the electroless plating step, there may be a step of performing electroplating (electroplating step) for the purpose of improving the properties of the conductive film.
In this step, after electroless plating in the electroless plating step, 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 to a thickness according to the purpose, and the electroless plating catalyst obtained by this aspect is suitable for 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. 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, from the viewpoint of conductivity, the film thickness when used for general electric wiring or the like is preferably 0.3 μm or more, and more preferably 3 μm or more.

  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.

  After the formation of the conductive film, the plating resist composed of the (C) layer and the unexposed portion of the (A) polymer precursor layer are not necessary, and a step of removing this can be performed. Peeling can be performed by spraying a stripping solution from the (C) layer surface side or immersing the formed substrate in the stripping solution. The stripping solution varies depending on the type of resist. Generally, a solvent or solution that swells the resist is used, and the stripping solution is wiped off by spraying or the substrate formed in the stripping solution is immersed in the resist. Swell and peel. At this time, the unexposed part of the (A) polymer precursor layer can also be peeled off simultaneously with the (C) layer. In the case of completely removing the remaining layer (A), it is preferable to repeat washing with water after applying the stripping solution.

As described above, 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, without roughening the surface of the insulating resin material layer having heat resistance and low dielectric constant such as epoxy resin, polyimide resin, liquid crystalline resin, polyarylene resin, etc. used as a substrate in the printed wiring board field, It can be used for forming a circuit made of a metal film material that exhibits high adhesion strength and has a sufficient thickness.
Using a conductive material such as a copper-clad laminate obtained by the production method of the present invention, for example, by a known etching process, the fineness of 20 microns or less, which has been difficult with conventional techniques, and adhesion strength High copper wiring can be formed.

(Manufacturing method of multilayer printed wiring board)
Next, an example is given and demonstrated about the manufacturing method of the multilayer printed wiring board using the laminated body for printed wiring boards of this invention.
When the laminate of the invention is bonded to the patterned inner circuit board, the protective film is removed, and then the insulating resin composition layer (insulating film) with a polymer precursor layer that is solid at room temperature from the support (base film) side Is laminated while being pressurized and heated. By laminating under conditions where the resin flow during lamination is greater than the conductor thickness of the inner layer circuit and half the depth of the through hole of the inner layer circuit and / or the depth of the surface via hole, Resin filling in the hole and / or the surface via hole can be performed simultaneously and collectively.
In addition, as the inner layer circuit board, glass epoxy, metal, polyester, polyimide, thermosetting polyphenylene ether, polyamide, polyaramid, paper, glass cloth, glass nonwoven fabric, liquid crystal polymer, etc. are used, and the resin is phenol resin, epoxy. A substrate using resin, imide resin, BT resin, PPE resin, tetrafluoroethylene resin, or the like as a resin can be used, and the circuit surface may be roughened or not processed in advance. .

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.

Generally, the resin can be satisfactorily filled with a plate thickness of about 1.4 mm or less and 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, if the conductor thickness of the inner layer circuit is thick, the surface smoothness and thickness of the resin on the pattern is not sufficient, or if the through hole and the surface via hole are large and deep, a dent is formed on the hole. If the laminate for multilayer printed wiring boards of the present invention is further laminated thereon, various conductor thicknesses and board thicknesses can be accommodated. After lamination, the support base film is peeled off after cooling to around room temperature.
After laminating the laminate for the printed wiring board on the inner layer circuit board, if necessary, a wiring pattern is formed on the heat-cured resin composition. Depending on the type of resin composition constituting the laminate for a wiring board, etc., and depending on the curing temperature of these forming materials, it is selected in the range of 20 to 120 minutes at 120 to 220 ° C.

  The wiring pattern is formed as follows. After lamination, the resin composition in the polymer precursor layer is heat-cured as necessary. The thermosetting conditions are selected at 120 to 220 ° C. for 20 to 120 minutes. After that, while peeling off the support film, or from above the support film, the portion that forms the conductive layer is irradiated with an actinic ray (for example, electron beam, UV light, etc.), and the graft polymer directly bonded to the insulating film surface is removed. Generate. Irradiation with actinic rays for producing the graft polymer may be performed immediately after lamination or after heat curing. 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 outermost photodegradable layer and irradiated through the pattern mask. Thereafter, the (C) layer solubilized by photolysis and the unreacted polymer precursor not involved in the formation of the graft polymer in the (A) layer are removed by development or washing treatment. The formation of the graft polymer and the removal of the unreacted material by the light irradiation may be performed after the next drilling step. Next, a predetermined through hole and / or via hole portion is drilled with a laser and / or a drill.

  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 drilling a through hole and / or via hole with a laser and / or a drill.

Next, an electroless plating catalyst or a precursor thereof is attached to the graft polymer generation region by the above-described method, and a wiring pattern (conductive layer) is formed by electroless plating. A more detailed method for forming a wiring pattern (conductive layer) by electroless plating is as follows.
In order to attach a plating catalyst to the graft polymer fixed on the insulating film, it is immersed in a plating catalyst solution (for example, a silver nitrate aqueous solution or a tin-palladium colloid solution). Palladium as an electroless plating catalyst. Metal beauty powders such as gold, platinum, silver, copper, nickel, cobalt, tin and / or their halides, oxides, hydroxides, sulfides, peroxides, amine salts, sulfates, nitrates, organic Examples thereof include acid salts and organic chelate compounds. 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 diameter of 0.1 to 50 μm.

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 is coated with the unsolubilized (C) layer, which is a plating resist, the plating catalyst cannot be fixed, and the plating catalyst solution is removed. Next, the electroless plating is performed 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 manner, 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 conductive layer is further increased. It can also be improved.
Finally, the (C) plating resist layer that is no longer needed can be removed.
When the printed wiring board laminate of the present invention is used, the resulting printed wiring board is excellent in surface smoothness. Therefore, the above-described production method is repeated a plurality of times, and the build-up layer is laminated in multiple stages to obtain a multilayer printed wiring board. It can also be manufactured.

  The laminate for a printed wiring board according to the present invention roughens the surface of the insulating film by using 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. This is useful for forming a printed wiring board and a flexible wiring board that exhibit high adhesion strength.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[Example 1]
(Synthesis example: Synthesis of polymer P-1 having a double bond)
Polyacrylic acid (average molecular weight 25000, Wako Pure Chemical Industries) 60 g and hydroquinone (Wako Pure Chemical Industries) 1.38 g (0.0125 mol) were placed in a 1 liter three-necked flask equipped with a condenser and N, N-dimethylacetamide. (DMAc, Wako Pure Chemical Industries) 700 g was added and stirred at room temperature to obtain a uniform solution. While stirring the solution, 64.6 g (0.416 mol) of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) was added dropwise. Subsequently, 0.79 g (1.25 × 10 ⁻³ mol) of di-n-butyltin dilaurate (Tokyo Chemical Industry) suspended in 30 g of DMAc was added dropwise. Heated in a 65 degree water bath with stirring. After 5 hours, the heating was stopped and the mixture was naturally cooled to room temperature. The reaction solution had an acid value of 7.105 mmol / g and a solid content of 11.83%.

300 g of the reaction solution was placed in a beaker and cooled to 5 degrees with an ice bath. While stirring the reaction solution, 41.2 ml of 4N aqueous sodium hydroxide solution was added dropwise over about 1 hour. The temperature of the reaction solution during the dropwise addition was 5 to 11 degrees. After the dropping, the reaction solution was stirred at room temperature for 10 minutes, and the solid content was removed by suction filtration to obtain a brown solution. The solution was reprecipitated with 3 liters of ethyl acetate, and the precipitated solid was collected by filtration. The solid was reslurried overnight with 3 liters of acetone. The solid was filtered off and vacuum dried for 10 hours to obtain a light brown powder P-1.
[Example 1]
(Production of reactive polymer composition laminate)
The following reactive polymer composition 1 was applied to the surface of a polyethylene terephthalate film having a thickness of 16 μm as a support with a rod bar so as to have a film thickness of 10 μm without any surface treatment or pretreatment. (C) The reactive polymer composition layer was provided by drying for minutes.

(Reactive polymer composition 1)
-77 parts of ethyl lactate-18.0 parts of the following binder P-2-4.5 parts of photoacid generator PAG-1-fluorinated surfactant (F-475, manufactured by Dainippon Ink & Chemicals, Inc.) 5 copies

(Production of graft precursor layer laminate)
On the reactive polymer composition of the reactive polymer composition film in which the (C) reactive polymer composition layer is provided on the surface of the polyethylene terephthalate film having a thickness of 16 μm, an acrylic group as a polymerizable compound is formed. And a liquid composition 1 having the following composition comprising a polymer having a carboxyl group as an interactive group (hydrophilic polymer having a polymerizable group in the side chain: P-1, obtained by the synthesis example described above) The graft polymer precursor layer was provided by coating at 100 ° C. and drying at 100 ° C. for 1 minute. The film thickness of the polymer precursor layer was adjusted to be in the range of 0.2 to 1.5 μm.
(Liquid composition 1 containing a polymerizable compound)
-Hydrophilic polymer (P-1) having a polymerizable group in the side chain 3.1 g
・ Water 24.6g
1-methoxy-2-propanol 12.3 g

(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 novolak resin (phenolic hydroxyl group equivalent 105, Phenolite manufactured 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., nonvolatile content 30% by mass, weight average molecular weight 47000) composed of Epicoat 828 and bisphenol S is added thereto. 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 applied on the polymer precursor layer of the film having the reactive polymer composition layer and the polymer precursor layer with a die coater so that the thickness after drying was 70 μm. The insulating resin composition film was obtained by drying at a temperature of from 120C to 120C.
(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, isopropymethylmetha-2-methyl-1,2-propylmethylmethacrylate-2-methyl-1,2-azomethyl-2-methyl-2-azomethyl-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.

  Furthermore, a 20 μm polypropylene film was disposed as a protective layer, and an insulating film, a polymer precursor layer, and a reactive polymer composition layer were formed on the support by coating, and the surface was covered with the protective layer. The laminated body 1 for printed wiring boards of this invention was obtained.

(Production of printed wiring board using laminate for printed wiring board)
(1) Application of laminate for printed wiring board on substrate Using laminate film 1 for printed wiring board obtained above, a substrate on which wiring is to be formed (patterned glass epoxy inner layer circuit board (conductor) The laminated film for printed wiring board is disposed on the thickness 18 μm) so that the protective layer is peeled off and the substrate and the insulating film are laminated, and a vacuum laminator is used at 100 MPa to 110 ° C. at a pressure of 0.2 MPa. It was made to adhere according to the conditions.
(2) Exposure (formation of plating resist and graft polymer)
Next, the support of the laminate 1 is peeled off, exposed in a pattern by the following method, washed, and a graft polymer is formed in a pattern on the insulating resin composition layer. A surface graft material in which the immature region was coated with the layer (C) was obtained.
The exposure was performed at room temperature for 1 minute using an exposure machine: an ultraviolet irradiation device (UVX-02516S1LP01, manufactured by USHIO INC.) So that the portion where the conductive layer was to be formed was exposed to light. After the exposure, it was thoroughly washed with pure water. By this exposure, decomposition of the (C) layer in the exposed region and generation of a graft polymer bonded to the (B) insulating film in the (A) layer are simultaneously performed. Separately, as a sample for measuring the adhesion strength, the entire surface was irradiated with light in an exposure machine, and after the exposure, it was sufficiently washed with pure water. By this exposure, the decomposition of the (C) layer on the entire surface and the generation of the graft polymer combined with the (B) insulating film in the (A) layer are simultaneously performed.

(Production of printed wiring board using laminate for printed wiring board)
(3) Adhesion and confirmation of electroless plating catalyst etc. Electroless plating catalyst is applied to the surface graft pattern material 1 obtained by the laminate of the present invention obtained as described above, and electroless plating is performed. Thus, the wiring board of Example 1 was obtained.
Separately, in order to measure the adhesion strength, a sample for adhesion measurement was obtained by applying an electroless plating catalyst to the sample that was similarly irradiated with light and performing electroless plating and electroplating. .
(Implementation of electroless plating and electrolytic plating process)
The surface graft pattern material 1 was immersed in a 0.1% by mass aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 hour, and then washed with distilled water. Then, it immersed in the electroless-plating bath of the following composition for 120 minutes, and the electroconductive pattern material of Example 1 was produced. The sample irradiated with light on the entire surface was immersed in a 0.1% by mass aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 hour, and then washed with distilled water. Then, after being immersed in an electroless plating bath having the following composition for 20 minutes, electroplating was carried out for 20 minutes in an electroplating bath having the following composition to obtain a sample for adhesion measurement.
<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 of conductive pattern material]
(Surface unevenness)
The surface unevenness of the obtained conductive material was measured with Nanopics (Nanopics 1000, manufactured by Seiko Instruments Inc., using DFM cantilever).
Surface roughness Rz = 50nm
(Measurement of metal film thickness)
Measurement was performed using a DFM cantilever.
(Adhesion strength evaluation)
A copper plate (thickness: 50 μm) was bonded to the surface of the conductive material on which the metal film was formed with an epoxy adhesive (Araldite, manufactured by Ciba Geigy), dried at 140 ° C. for 4 hours, and then subjected to a 90-degree peeling test based on JIS C6481. went. The peeling apparatus used was a tensile tester AGS-J manufactured by Shimadzu Corporation. The result was 0.8 kN / m.

  As is clear from the above results, the conductive material obtained by the production method of the present invention has small surface irregularities, a sufficient thickness on the smooth insulator layer surface, and adhesion to the substrate. It was found that an excellent metal film was formed.

(A)-(F) It is a schematic sectional drawing which shows the process of forming a conductive layer in a pattern form on the surface of a desired internal circuit board using the laminated body for printed wiring boards of this invention.

Explanation of symbols

10 Laminate for printed wiring boards (laminate)
DESCRIPTION OF SYMBOLS 12 Support body 14 Photodegradable layer 16 Polymer precursor layer 18 Insulating resin composition layer 20 Protective layer 22 Inner circuit board

Claims (9)

On the support, (B) an insulating resin composition layer containing a photopolymerization initiator, and (A) a polymer compound that reacts with the insulating resin composition layer by the action of the photopolymerization initiator. A reactive polymer precursor layer containing a compound that can be obtained, and (C) a positive-type reactive polymer composition layer containing a compound that decomposes upon exposure , and the layer (B) is formed on a substrate. A laminate for producing a printed wiring board , wherein the laminate is used so as to be in contact with each other . On the support, (B) an insulating resin composition layer containing a photopolymerization initiator, and (A) a polymer compound that reacts with the insulating resin composition layer by the action of the photopolymerization initiator. compound and the reactive polymer precursor layer containing that may, be a printed wiring board fabrication laminate that having a working and positive-reactive polymer composition layer containing a decomposed compound (C) exposure ,
On the support, the substrate has the (C) positive-type reactive polymer composition layer, the (A ) reactive polymer precursor layer, and the (B) insulating resin composition layer in sequence. A laminate for producing a printed wiring board, wherein the laminate is used by laminating the laminate. A protective film on the uppermost layer of the surface of the printed wiring board fabrication laminate was peeled off the support or the protective film, according to claim 1 or claim the exposed layer, characterized by using in lamination on the substrate Item 3. A laminate for producing a printed wiring board according to Item 2 . The printed wiring board production according to any one of claims 1 to 3 , wherein the reactive polymer precursor layer (A) contains a compound having a polymerizable double bond. Laminated body. The said (C) positive-type reactive polymer composition layer is a plating resist layer containing a photodegradable polymer compound, The any one of Claim 1 thru | or 4 characterized by the above-mentioned. Laminate for producing printed wiring boards. An exposure wavelength capable of generating reactive active species in the (B) insulating resin composition layer and an exposure wavelength capable of decomposing a compound that decomposes upon exposure in the (C) positive type reactive polymer composition layer. And (C) positive reaction by the reaction of the insulating resin composition layer (B) and the (A) reactive polymer precursor layer by the exposure of the wavelength. The laminate for producing a printed wiring board according to any one of claims 1 to 5 , wherein the decomposition of the compound decomposed by exposure in the conductive polymer composition layer occurs and proceeds simultaneously. (B) an exposure wavelength capable of generating reactive active species in the insulating resin composition layer, and an exposure wavelength capable of decomposing a compound decomposed by exposure in the (C) positive type reactive polymer composition layer. Are different from each other. First, the exposure region in the positive-type reactive polymer composition layer (C) is decomposed by exposure at a first wavelength, and then (B) is exposed by exposure at another wavelength. ) according to any one of claims 1 to 5, characterized in that to produce a high molecular compound by reaction of the insulating resin composition layer (a) the reactive polymer precursor layer Laminate for producing printed wiring boards. Using the laminate for producing a printed wiring board according to any one of claims 1 to 7, the (B) insulating resin composition layer and the (A) reactive polymer are formed on a substrate. A precursor layer, a step of laminating the (C) positive-type reactive polymer composition layer in this order, and a polymer compound that directly bonds to the (B) insulating resin composition layer by exposure. Forming a polymer generation region, attaching an electroless plating catalyst or a precursor thereof to the polymer generation region, and forming a circuit pattern by performing electroless plating. A method for producing a printed wiring board. After the step of forming the circuit pattern by performing the electroless plating, the unreacted (A) reactive polymer precursor layer and the (C) positive reactive polymer composition layer The method for producing a printed wiring board according to claim 8 , further comprising a removing step.

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