JP2008166435A - Method of manufacturing metal pattern material, and metal pattern material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a metal pattern material excellent in the ion migration resistance in a region wherein a metal pattern is not formed, and to provide the metal pattern material. <P>SOLUTION: The method of manufacturing the metal pattern material is characterized by comprising (a) the polymer layer forming step of forming a polymer layer on a substrate by forming a graft polymer having a functional group bonded directly to the surface of the substrate and interacting with an electroless plating catalyst or a precursor thereof, (b) the catalyst imparting step of imparting the electroless plating catalyst or the precursor thereof to the polymer layer, (c) the metal film forming step of forming a metal film on the whole surface of the polymer layer by carrying out the electroless plating, (d) the metal pattern forming step of forming the metal pattern by removing part of the metal film, and (e) the polymer layer removing step of removing the polymer layer existing in the region wherein the metal pattern is not formed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a metal pattern material and a metal pattern material, and more particularly to a method for manufacturing a metal pattern material and a metal pattern material suitable for forming a metal wiring board.

  2. Description of the Related Art Conventionally, a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.

  The adhesion between the substrate and the metal film in the metal pattern formation region is expressed by an anchor effect generated by providing irregularities on the substrate surface. For this reason, there is a problem that the high frequency characteristics when used as a metal wiring are deteriorated due to the unevenness of the obtained metal pattern at the substrate interface. In addition, in order to obtain a metal pattern with excellent adhesion between the metal film and the substrate, it is necessary to treat the substrate surface with a strong acid such as chromic acid in order to make the substrate surface uneven. There is a problem that a complicated process is necessary.

In order to solve this problem, plasma treatment is performed on the surface of the substrate, a polymerization initiating group is introduced on the surface of the substrate, a monomer is polymerized from the polymerization initiating group, and a surface graft polymer having a polar group is generated on the substrate surface. By performing this surface treatment, a method for improving the adhesion between the substrate and the metal film without roughening the surface of the substrate has been proposed (see, for example, Non-Patent Document 1).
However, when a part of the metal film obtained by applying this method is removed and used as a wiring of a metal wiring board, a graft polymer having a polar group remains in a non-formation region of the metal pattern, and moisture or Since ions and the like are easily retained, there is a concern about the migration resistance between the wirings.
Advanced Materials 2000 No. 20 1481-1494

The present invention has been made in view of the above-mentioned drawbacks of the prior art, and an object thereof is to achieve the following object.
That is, a first object of the present invention is to provide a method for producing a metal pattern material having excellent migration resistance.
The second object of the present invention is to provide a metal pattern material excellent in migration resistance.

  As a result of intensive studies in view of the above problems, the present inventor has found that the above object can be achieved by the following means.

<1> (a) Formation of a polymer layer on a substrate that forms a polymer layer by forming a graft polymer that is directly bonded to the surface of the substrate and has a functional group that interacts with an electroless plating catalyst or a precursor thereof. Process,
(B) a catalyst application step of applying an electroless plating catalyst or a precursor thereof to the polymer layer;
(C) a metal film forming step of plating and forming a metal film on the entire surface of the polymer layer;
(D) a metal pattern forming step of forming a metal pattern by removing a part of the metal film, and
(E) a polymer layer removing step for removing the polymer layer present in the non-formation region of the metal pattern;
A method for producing a metal pattern material, comprising:

  <2> The method for producing a metal pattern material according to <1>, wherein the polymer layer removing step is performed by hydrolysis.

  <3> The substrate is a substrate made of an insulating resin having a dielectric loss tangent at 1 GHz of 0.01 or less, or a substrate having a layer made of the insulating resin on a base material. The manufacturing method of the metal pattern material as described in 1> or <2>.

  <4> The substrate is a substrate made of an insulating resin having a dielectric constant of 3.5 or less at 1 GHz, or a substrate having a layer made of the insulating resin on a base material. The method for producing a metal pattern material according to any one of 1> to <3>.

  <5> The polymer layer forming step (a) is to apply energy after contacting a polymer having a functional group and a polymerizable group that interact with an electroless plating catalyst or a precursor thereof on a substrate. The method for producing a metal pattern material according to any one of <1> to <4>, wherein the polymer is directly bonded to the entire surface of the substrate.

  <6> The (a) polymer layer forming step includes (a-1) a step of producing a substrate on which a layer expressing the polymerization initiating ability is formed, and (a-2) the polymerization initiating ability. And a step of directly chemically bonding a polymer having a functional group and a polymerizable group that interacts with an electroless plating catalyst or a precursor thereof on a substrate on which a layer that expresses <1> is formed. > The manufacturing method of the metal pattern material of any one of <4>.

  <7> In the step (a-2), a polymer having a functional group and a polymerizable group that interacts with an electroless plating catalyst or a precursor thereof on a substrate on which a layer that exhibits the polymerization initiating ability is formed. The method for producing a metal pattern material according to <6>, wherein the polymer is directly bonded to the entire surface of the substrate by applying energy after the contact.

  <8> A metal pattern having a polymer layer made of a graft polymer directly chemically bonded to the substrate and a plating layer formed inside and on the polymer layer on the substrate, and a non-formation region of the metal pattern Is a region where the polymer layer is not present.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the metal pattern material excellent in migration resistance can be provided.
Moreover, according to this invention, the metal pattern material excellent in migration resistance can be provided.

[Method for producing metal pattern material]
In the method for producing a metal pattern material of the present invention, (a) a graft polymer that directly binds to the surface of the substrate and has a functional group that interacts with an electroless plating catalyst or a precursor thereof is formed on the substrate. A polymer layer forming step for forming a polymer layer; (b) a catalyst applying step for applying an electroless plating catalyst or a precursor thereof to the polymer layer; and (c) electroless plating to form a metal film on the entire surface of the polymer layer. A metal film forming step, (d) a metal pattern forming step for removing a part of the metal film to form a metal pattern, and (e) a polymer layer for removing a polymer layer present in a non-formation region of the metal pattern. A removal step.
It is characterized by that.

<(A) Polymer layer forming step>
In this step, a graft having a functional group (hereinafter, appropriately referred to as “interactive group”) that directly binds to the surface of the substrate and interacts with the electroless plating catalyst or a precursor thereof is formed on the substrate. A polymer is formed to form a polymer layer.
As the polymer layer forming step in the present invention, from the viewpoint of simplicity of process and suitability for industrialization, after bringing the polymer having an interactive group into contact with the substrate, energy is applied to the entire substrate surface. More preferably, it is a step of directly chemically bonding the polymer.
Hereinafter, the polymer layer forming step will be described in detail.

(Surface graft)
The production of the graft polymer in this step can be carried out using a means generally called surface graft polymerization.
In general, surface graft polymerization is a method of synthesizing a graft (graft) polymer by providing an active species on a polymer compound chain forming a solid surface and further polymerizing another monomer from the active species. It is.

In the present invention, an active site is generated on the substrate by bringing a polymerizable compound having an interactive group into contact with the substrate and applying energy thereto, and this active site and the polymerizable group of the polymerizable compound. React with each other to cause a surface graft polymerization reaction.
Moreover, after providing an energy and generating an active site on a board | substrate, you may make the polymeric compound which has an interactive group contact on the board | substrate.

This contact may be performed by immersing the substrate in a liquid composition containing a polymerizable compound having an interactive group, but from the viewpoint of handleability and production efficiency, as described later, It is preferable to use a method in which the liquid composition is applied to the substrate surface or the coating film is dried to form the graft polymer precursor layer.
In addition, when the graft polymer is generated on both sides of the substrate, the graft polymer may be generated simultaneously using the surface graft polymerization as described above, or after the graft polymer is first generated on one side, A graft polymer may be formed on the other side.

Any of the known methods described in the literature can be used as the surface graft polymerization method for realizing the present invention. For example, New Polymer Experimental Science 10, edited by Polymer Society of Japan, 1994, published by Kyoritsu Shuppan Co., Ltd., p135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods. In addition, the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, 1999.2, p203, p695 describes radiation-induced graft polymerization methods such as γ rays and electron beams.
As a specific method of the photograft polymerization method, methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used.

In the plasma irradiation graft polymerization method and the radiation irradiation graft polymerization method, the literatures described above and Y.C. Ikada et al, Macromolecules vol. 19, page 1804 (1986). Specifically, a graft polymer can be obtained by treating a polymer surface such as PET with plasma or electron beam, generating radicals on the surface, and then reacting the active surface with a nomer.
In addition to the above-mentioned documents, the photo-graft polymerization method is applied to the surface of a film substrate as described in JP-A-53-17407 (Kansai Paint) and JP-A-2000-212313 (Dainippon Ink). A graft polymer can be obtained by applying a photopolymerizable composition, then contacting a radical polymerization compound and irradiating light.

  The polymerizable compound having an interactive group used for the production of the graft polymer in the present invention is obtained using at least one selected from a monomer having an interactive group or a monomer having an interactive group. A polymer in which an ethylene addition polymerizable unsaturated group (polymerizable group) such as a vinyl group, an allyl group, or a (meth) acryl group is introduced into a homopolymer or copolymer as a polymerizable group (hereinafter referred to as “interactive group” as appropriate). For example, "containing polymerizable polymer"). The interactive group-containing polymerizable polymer has a polymerizable group at least at a terminal or a side chain.

Examples of the monomer having an interactive group include those shown below.
That is, for example, (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, N-monomethylol (meth) acrylamide, N-dimethylol Carboxyl group, sulfonic acid group, amino such as (meth) acrylamide, allylamine, 3-vinylpropionic acid or its alkali metal salt and amine salt, dimethylaminoethyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, etc. And monomers having a functional group such as a group and a hydroxyl group. These monomers may be used individually by 1 type, and may use 2 or more types together.

Moreover, an interactive group containing polymeric polymer is compoundable by using the synthesis | combining method shown below.
Synthesis methods include: i) a method of copolymerizing a monomer having an interactive group and a monomer having a polymerizable group at a specific position; ii) a monomer having an interactive group and a monomer having a double bond precursor; Iii) introducing a double bond by reacting a polymer having an interactive group and a monomer having a polymerizable group (polymerizable group) Method).
Among the above three methods, the methods ii) and iii) are preferable from the viewpoint of synthesis suitability.

  Examples of the monomer having a polymerizable group used in the synthesis method i) include the following compounds.

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

In the above formula, A ¹ is an organic group having a polymerizable group, R ^{1 to} R ³ are hydrogen atoms and / or monovalent organic groups, and X and Z are leaving groups removed by elimination reaction. Here, the elimination reaction means that Z is extracted by the action of a base and X is eliminated. X is preferably eliminated as an anion and Z as a cation.
Specific examples include the following compounds.

  In the synthesis method of ii), in order to convert a double bond precursor to a double bond, as shown below, a method for removing a leaving group represented by X and Z by an elimination reaction, That is, a reaction in which Z is extracted by the action of a base and X is eliminated is used.

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

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

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

In the synthesis method of iii), the monomer having a polymerizable group to be reacted with the polymer having an interactive group varies depending on the type of the functional group in the polymer having an interactive group, but the following functional groups are combined. Monomers having can be used.
That is, (functional group of polymer, functional group of monomer) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (hydroxyl group, carboxyl group), (hydroxyl group, epoxy group) ), (Hydroxyl group, isocyanate group) and the like.
Specifically, the following monomers can be used.

Moreover, when the interactive group containing polymeric polymer in this invention has a carboxylic acid group, you may convert into a carboxylate structure.
In addition, as a reagent for converting a carboxylic acid group into a carboxylate structure, an inorganic base or an organic base can be used. Preferably, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, Potassium bicarbonate.

  The useful weight-average molecular weight of the interactive group-containing polymerizable polymer thus synthesized is in the range of 500 to 500,000, and particularly preferably 5,000 to 250,000.

  Examples of the polymerizable compound having an interactive group that can be used to form a graft polymer include the above-described monomer having an interactive group, a polymerizable polymer containing an interactive group, and a macro having the same interactive group. Monomers can also be used.

  The graft polymer obtained from such a polymerizable compound may be a homopolymer of one of the polymerizable compounds having a functional group as described above, or may be a copolymer of two or more. Moreover, unless the effect of this invention is impaired, the copolymer with another polymeric compound may be sufficient.

The macromonomer having an interactive group can be prepared by a known method using the monomer having an interactive group described above. Specifically, the production method of the macromonomer used in the present invention is, for example, the second of “Macromonomer Chemistry and Industry” (editor, Yuya Yamashita) published on September 20, 1999 by the IP Publishing Office. Various proposals have been made in the chapter “Synthesis of Macromonomers”.
The useful weight average molecular weight of these macromonomers is in the range of 250 to 100,000, with a particularly preferred range being 400 to 30,000.

When contacting a polymerizable compound having such an interactive group on a substrate, a liquid composition containing the polymerizable compound having an interactive group is prepared and used as described above. That's fine. Alternatively, a liquid composition containing a polymerizable compound having an interactive group may be applied and dried.
The solvent used in preparing the liquid composition containing a polymerizable compound having such an interactive group is not particularly limited as long as the polymerizable compound having an interactive group as a main component can be dissolved. Moreover, you may add surfactant to this liquid composition as needed.
Examples of solvents that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, formamide, and dimethylacetamide. Examples thereof include amide solvents and water.

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

When a graft composition is formed by bringing a liquid composition into contact with a substrate by a coating method, or when a mode in which a graft polymer precursor layer is formed is used, the coating amount is a viewpoint of obtaining a sufficient coating film. Is preferably 0.1 to 10 g / m ^{2 in} terms of solid content, and more preferably 0.5 to 5 g / m ² .

-Energy provision-
As an energy application method for generating active sites on the substrate surface, for example, radiation irradiation such as heating or exposure can be used.
Specific examples of the energy applying means include, for example, light irradiation with a UV lamp, visible light, etc., heating with a hot plate, and further glow discharge treatment. Here, examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Further, g-line, i-line, and Deep-UV light are also used.
The time required for energy application varies depending on the intended radical generation amount on the substrate, the amount of graft polymer generated, and the energy application means, but is usually between 10 seconds and 5 hours.

  In addition, the thickness of the polymer layer in the present invention is preferably in the range of 0.1 to 3 μm, and in the range of 0.5 to 2 μm, from the viewpoint of sufficiently adsorbing the electroless plating catalyst or its precursor. More preferably.

(substrate)
The substrate used in the present invention will be described.
The substrate in the present invention refers to a substrate on which the graft polymer can be directly chemically bonded. For example, in the case where an intermediate layer such as a layer that exhibits polymerization initiating ability is provided on a base material to produce a graft polymer thereon, the substrate is the base material and the intermediate layer provided on the base material. In the case where the graft polymer is directly produced on the base material, the substrate means the base material itself. Here, the base material in this invention refers to the material itself which becomes a support body for forming a metal pattern on it.

In the present invention, from the viewpoint of efficiently generating active sites at the time of graft polymerization, a substrate obtained by forming a layer that exhibits polymerization initiating ability on the substrate [(a-1) step] is obtained. It is preferable to use it.
In the present invention, when a substrate having a layer exhibiting a polymerization initiating ability containing a polymerization initiator is used as a substrate [step (a-1)], the polymerization initiating ability is exhibited. An embodiment in which the interactive group-containing polymerizable polymer is directly chemically bonded onto the layer [(a-2) step] is preferable. In addition, as the step (a-2), a layer that expresses the polymerization initiating ability by applying energy after contacting the interactive group-containing polymerizable polymer on the layer that expresses the polymerization initiating ability. It is preferred that the polymer is directly chemically bonded to. That is, after an interactive group-containing polymerizable polymer is brought into contact with a layer that exhibits polymerization initiating ability, energy is imparted to the layer that exhibits the initiating ability to generate active species (radicals), and polymerization is performed. It is a preferred embodiment that a method of polymerizing the surface of the layer expressing the initiating ability with the interactive group-containing polymerizable polymer is used.

Hereinafter, the substrate applicable to the present invention will be described in more detail.
The substrate in the present invention is a dimensionally stable plate-like material, and any substrate can be used as long as necessary flexibility, strength, durability and the like are satisfied, and is appropriately selected according to the purpose of use.
Specific materials that can be applied to the substrate include polyimide resin, bismaleimide resin, polyphenylene oxide resin, epoxy resin, liquid crystal polymer, polytetrafluoroethylene resin, etc., and silicone substrates, paper, and plastic laminates. Examples thereof include paper, metal plates (for example, aluminum, zinc, copper, etc.), paper or plastic films on which the above metals are laminated or vapor-deposited.

Moreover, when producing a printed wiring board using the metal pattern material obtained by this invention, it is preferable to use insulating resin as a material applicable to a board | substrate.
Examples of such insulating resins include resins such as polyphenylene ether or modified polyphenylene ether, cyanate ester compounds, and epoxy compounds. As a board | substrate in this invention, what is formed with the thermosetting resin composition containing 1 or more types of these resin is used preferably. Preferred combinations when two or more of these resins are combined to form a resin composition include polyphenylene ether or modified polyphenylene ether and cyanate ester compound, polyphenylene ether or modified polyphenylene ether and epoxy compound, polyphenylene ether or modified polyphenylene ether and cyanate. Examples include combinations of ester compounds and epoxy compounds.
When forming a substrate of a multilayer printed wiring board with such a thermosetting resin composition, it is preferable not to include an inorganic filler selected from the group consisting of silica, talc, aluminum hydroxide, magnesium hydroxide, Moreover, it is preferable that it is a thermosetting resin composition which further contains a bromine compound or a phosphorus compound.

Other insulating resins that can be suitably used for printed wiring board substrates include 1,2-bis (vinylphenylene) ethane resin, or modified resins of this and polyphenylene ether resins. Is described in detail in, for example, Satoru Amaha et al., “Journal of Applied Polymer Science” Vol. 92, p1252-1258 (2004).
Furthermore, a liquid crystalline polymer that can be obtained as a commercial product under the name of Kuraray Bexter or a fluororesin typified by polytetrafluoroethylene (PTFE) is also preferred.
Of these resins, fluororesin (PTFE) is most excellent in high frequency characteristics among polymer materials. However, since it is a thermoplastic resin having a low Tg, the dimensional stability against heat is poor, and the mechanical strength is inferior to that of the thermosetting resin material. There is also a problem that the formability and workability are poor. A thermoplastic resin such as polyphenylene ether (PPE) can also be used after being alloyed with a thermosetting resin. For example, it can be used as an alloyed resin of PPE and epoxy resin, triallyl isocyanate, or an alloyed resin of PPE resin introduced with a polymerizable functional group and other thermosetting resins.
Epoxy resins have insufficient dielectric properties as they are, but improvements have been made through the introduction of bulky skeletons. In this way, the introduction and modification of structures that make use of the properties of each resin to compensate for its drawbacks. The resin which performed etc. is used preferably.
For example, cyanate ester is a resin having the most excellent dielectric properties among thermosetting, but is rarely used alone, and is used as a modified resin such as an epoxy resin, a maleimide resin, and a thermoplastic resin. These details are described in “Electronic Technology”, No. 9, 2002, p35, and these descriptions can also be referred to in selecting such an insulating resin.

  In the case of forming a printed wiring board using the metal pattern material obtained by the present invention, in order to suppress delay and attenuation of a signal from the viewpoint of processing a large amount of data at a high speed, a dielectric constant and a dielectric loss tangent. It is effective to lower each. The use of low dielectric loss tangent material is as described in detail in "Journal of Electronics Packaging Society" Vol. 7, No. 5, P397 (2004), and in particular, an insulating material having low dielectric loss tangent characteristics is adopted. It is preferable to increase the speed.

Specifically, the substrate in the present invention is a substrate made of an insulating resin having a dielectric constant at 3.5 GHz of 1 GHz or a substrate having a layer made of the insulating resin on a base material. preferable. Moreover, it is preferable that it is a board | substrate which has a board | substrate consisting of insulating resin which is 3.5 or less, or a layer which consists of this insulating resin on a base material.
In particular, the substrate in the present invention is a substrate made of an insulating resin having a dielectric constant (relative dielectric constant) of 3.5 or less at 1 GHz and an insulating resin having a dielectric loss tangent of 0.01 or less at 1 GHz. More preferably.

  The dielectric constant and dielectric loss tangent of the insulating resin are measured using a cavity resonator perturbation method based on a conventional method, for example, the method described in “18th Annual Meeting of the Electronics Packaging Society”, p189. It can be measured using a device (εr for ultra-thin sheet, tan δ measuring device / system, manufactured by Keycom Corporation).

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

-Substrate surface or intermediate layer-
As described above, the substrate in the present invention has a surface on which the graft polymer can be directly chemically bonded, and the surface of the substrate itself may have such characteristics. An intermediate layer having various characteristics may be provided on the surface of the base material to form a substrate.

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

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

  The layer expressing the polymerization initiating ability includes i) a polymerizable layer containing a polymerizable compound and a polymerization initiator, and ii) a polymer having a functional group and a crosslinkable group having a polymerization initiating ability in the side chain (hereinafter, specified) There are two modes: a polymerization initiating layer formed by immobilizing a polymerization initiating polymer) by a crosslinking reaction. The layers that exhibit the polymerization initiating ability of these two embodiments will be described sequentially.

i) Polymerizable layer containing a polymerizable compound and a polymerization initiator The polymerizable layer is prepared by dissolving necessary components such as a polymerizable compound and a polymerization initiator in a solvent capable of dissolving them, and then applying the substrate by a method such as coating. It can be formed on the surface and hardened by heating or light irradiation.

(A) Polymerizable compound The polymerizable compound used in the polymerizable layer has good adhesion to the substrate, and a monomer or polymer having a hydrophilic group can be added by applying energy such as actinic ray irradiation. Although there will be no restriction | limiting in particular if it is a thing, Among these, the hydrophobic polymer which has a polymeric group in a molecule | numerator is preferable.
Specific examples of such hydrophobic polymers include diene homopolymers such as polybutadiene, polyisoprene, and polypentadiene, and allyl groups such as allyl (meth) acrylates and 2-allyloxyethyl methacrylates. Monomer homopolymer;
Furthermore, binary or multicomponent with styrene, (meth) acrylic acid ester, (meth) acrylonitrile, etc. containing diene monomer such as polybutadiene, polyisoprene, polypentadiene or allyl group-containing monomer as a constituent unit. Copolymer;
And linear polymers or three-dimensional polymers having a carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, and high-density polyethylene.
In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.
The content of the polymerizable compound is preferably in the range of 0 to 100% by mass and particularly preferably in the range of 10 to 80% by mass in terms of solid content in the polymerizable layer.

(B) Polymerization initiator The polymerizable layer in the present invention preferably contains a polymerization initiator for expressing the polymerization initiating ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, or the like that can exhibit polymerization initiating ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Can be selected and used as appropriate. Among these, use of photopolymerization having a higher reaction rate (polymerization rate) than thermal polymerization is preferable from the viewpoint of production suitability, and therefore, a photopolymerization initiator is preferably used.
The photopolymerization initiator is active with respect to the actinic ray to be irradiated, and is capable of polymerizing a polymerizable compound contained in the polymerizable layer and a monomer or polymer having a hydrophilic group. There is no particular limitation, and for example, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator and the like can be used.

Specific examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Acetophenones such as: benzophenone (4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, ketones; benzoin, benzoin methyl ether, benzoin isopropyl Examples thereof include benzoin ethers such as ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone, and the like.
The content of the polymerization initiator in the polymerizable layer is preferably in the range of 0.1 to 70% by mass and particularly preferably in the range of 1 to 40% by mass in terms of solid content.

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

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

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

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

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

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

(C) Film formation of polymerization initiation layer The polymerization initiation layer is prepared by dissolving the above-mentioned specific polymerization initiation polymer in an appropriate solvent, preparing a coating solution, and placing the coating solution on a substrate by coating or the like, and removing the solvent. Then, a film is formed as the crosslinking reaction proceeds. That is, the specific polymerization initiating polymer is immobilized by the progress of the crosslinking reaction. The immobilization by the crosslinking reaction includes a method using a self-condensation reaction of a specific polymerization initiating polymer and a method using a crosslinking agent in combination, and a crosslinking agent is preferably used. As a method of using the self-condensation reaction of the specific polymerization initiating polymer, for example, when the crosslinkable group is —NCO, the method uses the property that the self-condensation reaction proceeds by applying heat. As this self-condensation reaction proceeds, a crosslinked structure can be formed.

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

  Specific examples of the crosslinking agent include those having the structures shown below.

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

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

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

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

-Substrate having polymerization initiation ability-
As a substrate used in the polymer layer forming step, the substrate itself may have a polymerization initiating ability. As such a substrate, for example, a substrate containing polyimide having a polymerization initiation site in the skeleton is suitable. Examples of the substrate containing polyimide having a polymerization initiation site in the skeleton include those described in paragraph numbers [0028] to [0088] of JP-A-2005-281350.

  Specific examples of polyimide having a polymerization initiation site in the skeleton are shown below, but are not limited thereto.

  As described above, a substrate containing a specific polyimide (a polyimide substrate having a polymerization initiating ability) is obtained.

  Subsequent to the “polymer layer forming step” described above, a “catalyst applying step”, a “metal film forming step”, a “metal pattern forming step”, and a “polymer layer removing step” are performed. A metal pattern (conductive pattern) having excellent adhesion to the substrate is formed.

<(B) Catalyst application step>
In this step, an electroless plating catalyst or a precursor thereof is imparted to the graft polymer produced as described above.
Thereby, the interactive group which the graft polymer has, and the electroless plating catalyst or its precursor interact and are adsorbed.

(Electroless plating catalyst)
The electroless plating catalyst that can be 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 technique for adsorbing the zero-valent metal to the hydrophilic group, for example, a technique in which a metal colloid whose charge is adjusted so as to interact with the hydrophilic group is applied to the surface on which the graft polymer is generated 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 controlled by the surfactant or the protective agent used here, and the metal colloid whose charge is controlled in this way interacts with the hydrophilic group of the graft polymer, thereby grafting. Metal colloid (electroless plating catalyst) can be adsorbed to the polymer.

(Electroless plating catalyst precursor)
The electroless plating catalyst precursor that can be 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. After the metal ions that are the electroless plating catalyst precursor are adsorbed to the hydrophilic group of the graft polymer and before being immersed in the electroless plating bath, they can be converted into a zero-valent metal by a separate reduction reaction. 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, MCn, M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.

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

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

(Electroless plating)
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
The electroless plating in this step is, for example, after removing the excess electroless plating catalyst (metal) by washing the substrate provided with the electroless plating catalyst obtained in the electroless plating catalyst application step, etc. It is performed by immersing in an electroless plating bath. As the electroless plating bath to be used, a generally known electroless plating bath can be used.
In addition, when the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is attached to or impregnated with the graft polymer, the substrate is washed with water to remove 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.
Known types of metals used in the electroless plating bath include copper, tin, lead, nickel, gold, palladium, rhodium, etc. Among them, 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 CuSO ₄ 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. Further, 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 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, or the temperature of the plating bath. Is preferably 0.5 μm or more, more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

  The metal film obtained as described above is formed by electroless plating with respect to an electroless plating catalyst adsorbed on a highly mobile graft polymer, and the plating solution is formed inside the layer made of the graft polymer. Therefore, the interface between the metal film and the substrate is expected to be in a hybrid state of the graft polymer and the electroless plating catalyst or the deposited plating metal. When a cross section of such a metal film is observed with an SEM, electroless plating catalyst and fine particles of the plating metal are dispersed in the layer made of the graft polymer, and further, relatively large metal particles are deposited thereon. It was confirmed that As shown in this result, since the interface is configured in a hybrid state of the graft polymer and fine particles, the unevenness difference of the interface between the substrate (organic component) and the inorganic material (electroless plating catalyst or plating metal) is 500 nm or less. Furthermore, even in a flat state of 100 nm or less, which is a preferred embodiment, the adhesion of the metal film was good.

  Here, the state of fine particles such as an electroless plating catalyst and a metal deposited by plating in the layer made of the graft polymer will be described in more detail. In the layer made of such a graft polymer, fine particles made of electroless plating catalyst, metal salt derived from electroless plating catalyst precursor, and / or metal deposited by electroless plating are dispersed. The dispersion state of the fine particles at this time becomes higher as it approaches the interface with the metal film, and there is a region containing 25% by volume or more of fine particles in the vicinity of the interface with the metal film. It is preferable from the viewpoint of expression, more preferably 30% by volume or more, more preferably 40% by volume or more, particularly preferably 50% by volume or more. Further, in the layer composed of the graft polymer, the region where such fine particles exist at a high density is preferably present in a region having a depth of 0.05 μm or more from the interface with the metal film toward the substrate. More preferably, it exists in a region of 1 μm or more, more preferably in a region of 0.2 μm or more, and particularly preferably to a depth of 0.3 μm or more.

<(D) Metal pattern formation process>
In this step, a part of the metal film formed in the metal film forming step is removed to form a metal pattern.
The removal of the metal film in this step can be performed by etching the metal film into a pattern. A generally known subtractive method or semi-additive method can be used for the etching process. A subtractive method is preferably used for removing the metal film in this step.

Hereinafter, a subtractive method suitable for this step will be described.
The subtractive method is (i) formation of a photosensitive resist film on a metal film (plating film) → (ii) pattern exposure and development to form a resist pattern of the metal film to be left behind → (iii) etching In (iv), the photosensitive resist layer is removed to form a metal pattern in which the metal film remains in a pattern.
The thickness of the metal film when the subtractive method is applied is preferably 5 μm or more, and more preferably in the range of 5 to 30 μm.
Hereinafter, a series of processes (i) to (iv) in the subtractive method will be described.

(I) Formation of photosensitive resist film As the photosensitive resist used for forming the photosensitive resist film, a photocurable negative resist or a photodissolvable positive resist that dissolves upon exposure can be used. The types of photosensitive resist are: 1. photosensitive dry film resist (DFR); 2. liquid resist; An ED (electrodeposition) resist is mentioned. Each of these has its own characteristics. 1. A photosensitive dry film resist (DFR) can be used in a dry manner, so that it is easy to handle. Since the liquid resist can be a thin photosensitive resist film, a pattern with good resolution can be formed. 3. The ED (electrodeposition) resist can be a thin photosensitive resist film, so that a pattern with good resolution can be made, and the followability to the unevenness of the coated surface is good and adhesion is excellent. . The photosensitive resist to be used may be appropriately selected in consideration of these characteristics. Hereinafter, formation of the photosensitive resist film will be described.

1. A photosensitive dry film generally has a sandwich structure sandwiched between a polyester film and a polyethylene film. Therefore, a method of pressure bonding with a hot roll while peeling the polyethylene film with a laminator on the metal film of the conductive film is used. Use.
2. The liquid resist is applied on the metal film of the conductive film and dried. As a coating method, spray coating, roll coating, curtain coating, or dip coating is used. Moreover, in order to apply | coat both surfaces of an electrically conductive film simultaneously, it is preferable to use a roll coat and a dip coat among these.
3. An ED (electrodeposition) resist is a colloid obtained by suspending a photosensitive resist in finely charged particles and suspending it in water. Therefore, ED (electrodeposition) resist is applied on the metal film of the conductive film, voltage is applied to the metal film, the particles are electrophoresed, the photosensitive resist is deposited on the metal film, and they are bonded to each other The method of making it into a film is used.

(Ii) Pattern exposure and development Pattern exposure is performed by bringing a mask film or a dry plate into close contact with the photosensitive resist film, and exposing with light in the photosensitive region of the photosensitive resist being used. In the case of using a mask film, the photosensitive resist film and the mask film are brought into close contact with each other with a vacuum baking frame and exposed. Regarding the exposure source, a point light source can be used when the pattern width is about 100 μm. Further, when a pattern having a pattern width of 100 μm or less is formed, a parallel light source is preferably used.

  For development, an unexposed portion can be used if it is a photo-curing negative resist, or anything that can dissolve an exposed portion if it is a photo-dissolving positive resist that dissolves upon exposure, Organic solvents and alkaline aqueous solutions are used. In recent years, alkaline aqueous solutions have been used to reduce environmental impact.

(Iii) Etching After the development is completed, the exposed metal film without the photosensitive resist film is chemically dissolved to form a metal pattern. Etching is performed mainly by spraying an etching solution from above and below with a horizontal conveyor device.
The etching solution oxidizes and dissolves the metal constituting the metal film with an oxidizing aqueous solution. Examples of the etching solution include ferric chloride solution, cupric chloride solution, and alkali etchant. Since the remaining photosensitive resist film may be peeled off by alkali, a ferric chloride solution and a cupric chloride solution are mainly used.

(Iv) Stripping of photosensitive resist film After etching is completed and the metal pattern is completed, the remaining photosensitive resist film is stripped. Stripping of the photosensitive resist film can be performed by spraying a stripping solution. The stripping solution varies depending on the type of resist, but generally a solvent that swells the photosensitive resist film is used.

  By this series of treatments, the metal film is removed in this step, whereby a desired metal pattern is formed.

<(E) Polymer layer removal step>
In this step, after forming the metal pattern in the metal pattern forming step, the polymer layer present in the non-formation region of the metal pattern is removed.

  If the graft polymer having an interactive group formed in the polymer layer forming step is present in the non-formed portion of the metal pattern (between the metal patterns), it may cause ion migration, but in this step the metal pattern is not formed. By removing the polymer layer present in the region, the ion migration resistance in the region can be improved. Therefore, if the method for producing a metal pattern material of the present invention is applied to, for example, the production of a wiring board, the electrical insulation between the formed metal wirings can be improved.

As a method for removing the polymer layer existing in the non-formation region of the metal pattern, any method can be used as long as it can remove the polymer layer. Specifically, there is a method of oxidizing and decomposing the polymer layer with a KMnO ₄ solution or a chromic acid solution, and a method of decomposing and removing a crosslinked structure by hydrolyzing an ester bond or the like in the polymer structure. There is.
As a method for removing the polymer layer in the present invention, removal by hydrolysis is more preferable from the viewpoints of stability of the treatment liquid, safety, and work safety.

As a method for hydrolyzing the polymer layer, (1) a method by alkali hydrolysis using an alkali metal hydroxide represented by NaOH or the like [hereinafter referred to as method (1). ], (2) A method by acid hydrolysis using a strong acid aqueous solution such as sulfuric acid / hydrochloric acid [hereinafter referred to as method (2). ], (3) Method using metal hydride such as lithium aluminum hydride [hereinafter referred to as method (3). And the like.
Hereinafter, specific processing conditions and the like of the methods (1) to (3) will be described. In the process shown below, the polymer layer present in the metal pattern formation region is not removed because the metal pattern becomes a resist, and only the polymer in the metal pattern non-formation region is processed. However, if the conditions are severer than appropriate processing conditions, the polymer layer in the metal pattern formation region may be exposed to the processing solution after the polymer in the non-metal pattern formation region is removed. It is preferable to perform the processing within appropriate processing conditions.

-Method (1)-
When performing alkali hydrolysis using an alkali metal hydroxide, an alkali solution in which the alkali metal hydroxide is dissolved in a solvent is used. As the solvent, water is preferable. Moreover, as a density | concentration of the hydroxide of the alkali metal in an alkaline solution, 0.1-10 mol% aqueous solution is preferable, More preferably, it is 0.5-5 mol%. It is preferable that the alkali metal hydroxide concentration in the alkaline solution be in this range because the hydrolysis reaction proceeds rapidly and the polymer layer portion in the metal pattern formation region is not damaged.
As a method of hydrolysis treatment, 1. 1. a method of immersing a substrate in an alkaline solution; A method of spraying an alkaline solution with a spray or the like can be used.
In the method of immersing the substrate in the alkaline solution, the immersion time is preferably 10 minutes to 5 hours, more preferably 10 minutes to 2 hours. Moreover, as temperature at the time of immersion, 20 to 80 degreeC is preferable, More preferably, it is 30 to 60 degreeC.
The method of spraying the alkaline solution with a spray or the like is preferable in that a fresh solution can always be supplied to the polymer in the nonmetallic pattern region, although the apparatus is complicated.

-Method (2)-
Examples of the acid that can be used for acid hydrolysis using a strong acid aqueous solution include hydrochloric acid, sulfuric acid, methanesulfonic acid, and nitric acid, and sulfuric acid, methanesulfonic acid, and nitric acid that are liquid at room temperature are preferable. As a density | concentration of strong acid aqueous solution, 0.1-10 mol% aqueous solution is preferable, More preferably, it is 0.5-5 mol%. When the concentration of the strong acid aqueous solution is within this range, the acid hydrolysis reaction proceeds rapidly and the polymer layer portion in the metal pattern formation region is not damaged, which is preferable.
As a method of acid hydrolysis treatment, 1. 1. a method of immersing a substrate in a strong acid aqueous solution; A method of spraying a strong acid aqueous solution with a spray or the like can be used.
In the method of immersing the substrate in the strong acid aqueous solution, the immersion time is preferably 10 minutes to 5 hours, more preferably 10 minutes to 2 hours. Moreover, as temperature at the time of immersion, 20 to 80 degreeC is preferable, More preferably, it is 30 to 60 degreeC.
The method of spraying a strong acid aqueous solution with a spray or the like is complicated in terms of apparatus, but is preferable in that a fresh solution can always be supplied to the polymer in the nonmetallic pattern region.
Since the metal surface may be discolored by acid corrosion, it is necessary to prevent corrosion of the metal surface by acid such as rust prevention treatment when this method is used.

-Method (3)-
In the case of using a metal hydride such as lithium aluminum hydride, a dehydrated organic solvent is used as the solvent because the metal hydride is decomposed by moisture. Examples of the organic solvent that can be used include ether, THF, dioxolane and the like. The concentration of the solution is preferably a 0.1 to 5 mol% aqueous solution, more preferably 0.5 to 2 mol%.
As a treatment method, a method of immersing the substrate in a solution can be used, and the immersion time is preferably 10 minutes to 5 hours, more preferably 10 minutes to 2 hours. Moreover, as temperature at the time of immersion, 0 to 50 degreeC is preferable, More preferably, it is 0 to 30 degreeC.

  As the hydrolysis method applicable to the present invention, among the above methods (1) to (3), the method (1) is preferable from the viewpoint of hydrolysis efficiency and suppression of side reactions.

In order to hydrolyze and remove the polymer layer, the crosslinking point of the graft polymer constituting the polymer layer needs to be a functional group capable of hydrolysis such as an ester bond. This is because the removal of the polymer layer in the present invention is performed by improving the solubility of the polymer layer by cutting the crosslinking point. For example, in the case of the polymer layer formed from the interactive group-containing polymerizable polymer in the present invention, the polymer layer has a side chain of the interactive group-containing polymerizable polymer due to radicals generated by exposure. When the polymerizable group reacts and crosslinks, a strong polymer layer having excellent adhesion to the substrate is formed. In this case, the polymerizable group in the side chain of the interactive group-containing polymerizable polymer is bonded to the polymer main chain with an ester bond, so that the crosslinking point is cut by hydrolysis, and the solubility of the polymer layer is reduced. Thus, the polymer layer in the metal pattern non-formation region can be easily removed.
In other words, a polymer layer in which a polymer having a functional group that interacts with an electroless plating catalyst or its precursor and a polymerizable group linked by an ester group is directly bonded to a substrate is used for hydrolysis removal of the polymer layer. is necessary.

<Other optional processes>
The method for producing a metal pattern material of the present invention is an essential step, the above-described (a) polymer layer forming step, (b) catalyst applying step, (c) metal film forming step, (d) metal pattern forming step, and (E) In addition to the polymer layer removal step, other optional steps such as an electroplating step and a rust prevention treatment step may be included as necessary.

(1) Electroplating step In the present invention, (c) between the metal film forming step and (d) the metal pattern forming step, or (d) as one of the steps included in the metal pattern forming step, or ( d) After the metal pattern forming step, a step of performing electroplating (electroplating step) may be included. More preferably, the electroplating step is performed between (c) the metal film forming step and (d) the metal pattern forming step. In this step, the metal film obtained by electroless plating in the metal film forming step is used as an electrode, and electroplating is further performed.

  In the electroplating step, a metal film having an arbitrary thickness can be easily formed on a metal film obtained by electroless plating and having excellent adhesion to the substrate. In the present invention, by adding this step, the metal film can be formed with a thickness according to the purpose, and the metal pattern material obtained in the present invention is suitable for various applications.

  A conventionally known method can be used as the electroplating method. In addition, as a metal used for electroplating, copper, chromium, lead, nickel, gold | metal | money, silver, tin, zinc etc. are mentioned, Copper, gold | metal | money, silver is preferable from a conductive viewpoint, and copper is more preferable.

  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, in order to use it when producing a general metal wiring or the like, the film thickness is preferably 0.3 μm or more, and more preferably 3 μm or more, from the viewpoint of conductivity.

(2) Rust prevention process In this invention, the rust prevention process for preventing oxidation can be performed with respect to the formed metal film (metal pattern).

  As the rust prevention treatment applicable to the present invention, any of the rust prevention treatment methods usually used at the time of producing a printed wiring board can be used. For example, a method of plating zinc on a substrate, a method of applying a flux, a method of applying a solder resist, or the like can be used.

[Metal pattern material]
The metal pattern material of the present invention has a metal pattern on a substrate having a polymer layer made of a graft polymer that is directly chemically bonded to the substrate and a plating layer formed inside and on the polymer layer. The pattern non-formation region is a region where the polymer layer does not exist, and can be suitably obtained by the metal pattern manufacturing method of the present invention described above.

In the metal pattern material of the present invention, since there is no polymer layer composed of a graft polymer having an interactive group in a non-formation region of the metal pattern, the metal migration that can occur due to the presence of the graft polymer is effective. Can be suppressed. Therefore, when the metal pattern material of the present invention is applied to a wiring board, a wiring board having high electrical insulation between metal wirings can be obtained.
In addition, the metal pattern region in the metal pattern material of the present invention is excellent in high frequency characteristics because the graft polymer constituting the polymer layer is directly bonded to the substrate surface and does not require roughening of the substrate surface. Have Furthermore, since the metal pattern region is firmly adhered to the substrate surface so as not to be peeled off even by mechanical operation such as rubbing, and has a homogeneous metal film, the metal pattern material of the present invention comprises: It is also suitably used for flexible metal wiring boards.
In addition, the metal pattern material of the present invention can be used for, for example, an electromagnetic wave prevention film and an antenna.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

[Preparation of substrate 1]
Liquid bisphenol A type epoxy resin (epoxy equivalent 176, manufactured by Japan Epoxy Resins Co., Ltd., Epicoat 825), triazine structure-containing phenol novolac resin MEK varnish (produced by Dainippon Ink and Chemicals, Phenolite LA-7052, Non-volatile content 62%, non-volatile phenolic hydroxyl group equivalent 120) 2 g, phenoxy resin MEK varnish (manufactured by Tohto Kasei Co., Ltd., YP-50EK35, non-volatile content 35%) 10.7 g, the following compound (1) as a polymerization initiator 2.3 g, MEK 5.3 g, and 2-ethyl-4-methylimidazole 0.053 g were mixed, stirred and completely dissolved to prepare a polymerization initiation layer coating solution 1.

  The epoxy resin composition was bar coated on a 128 μm thick polyimide film (manufactured by Toray DuPont, Kapton 500H) and dried at 170 ° C. for 30 minutes to form a polymerization initiation layer on the substrate. . The film thickness of the obtained polymerization initiation layer was 10 μm. The substrate thus obtained was designated as substrate 1.

[Production of Substrate 2]
The following polymerization initiation layer coating solution 2 was applied onto a polyimide film (product name: Kapton 500H, manufactured by Toray DuPont) using a rod bar No. 18, and dried at 80 ° C. for 2 minutes.
Next, this coated film was irradiated for 10 minutes using a 400 W high-pressure mercury lamp (UVL-400P, manufactured by Riko Kagaku Sangyo Co., Ltd.) and precured to form a polymerization initiation layer on the substrate. . The film thickness of the obtained polymerization initiation layer was 6.5 μm. The substrate thus obtained was designated as substrate 2.

<Polymerization initiation layer coating solution 2>
・ Allyl methacrylate / methacrylic acid copolymer 4g
(Molar ratio 80/20, molecular weight 100,000)
・ Ethylene oxide modified bisphenol A diacrylate 4g
(Toagosei Co., Ltd. M210)
・ 1.6g of 1-hydroxycyclohexyl phenyl ketone
・ 16 g of 1-methoxy-2-propanol

[Production of Substrate 3]
<Synthesis of polyimide precursor (polyamic acid)>
Under nitrogen, 4,4′-diaminodiphenyl ether (28.7 mmol) was dissolved as a diamine compound in N-methylpyrrolidone (30 ml) and stirred at room temperature for about 30 minutes. To this solution was added 3,3 ′, 4,4 ″ -benzophenonetetracarboxylic dianhydride (28.7 mmol) at 0 ° C. and stirred for 5 hours. The reaction solution was reprecipitated to obtain polyimide precursor 1. The structure of the product was confirmed by ¹ H-NMR and FT-IR.
The polyamic acid synthesized by the above method was dissolved in DMAc (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a 30% by mass solution to obtain a polymerization layer coating solution 3. The solution is applied to a glass substrate using a rod bar # 36, dried at 100 ° C. for 5 minutes, heated at 250 ° C. for 30 minutes to solidify, and then peeled off from the glass substrate. A substrate 3 made of polyimide) was obtained.

[Production of Substrate 4]
On the polyimide film (product name: Kapton 500H, manufactured by Toray DuPont), the following polymerization initiation layer coating solution 4 was applied using a rod bar No. 18, and dried and crosslinked at 110 ° C. for 10 minutes. The film thickness of the obtained polymerization initiation layer was 9.3 μm. The substrate thus obtained was designated as substrate 4.

(Polymerization initiation layer coating solution 4)
・ The following polymerization initiating polymer A 0.4 g
・ TDI (Tolylene-2,4-diisocyanate) 0.16g
・ Methyl ethyl ketone (MEK) 1.6g

(Synthesis of polymerization initiating polymer A)
30 g of propylene glycol monomethyl ether (MFG) was added to a 300 ml three-necked flask and heated to 75 ° C. [2- (Acryloyloxy) ethyl] (4-benzoylbenzyl) dimethyl ammonium bromide 8.1g, 2-Hydroxyethylmethacrylate, 9.9g, isopropymethylmethacrylate-2dimethyl,
A solution of 0.43 g of azobis (2-methylpropionate) and 30 g of MFG 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 the following specific polymerization initiating polymer A. In addition, the numerical value attached | subjected to the following structural formula shows the molar copolymerization ratio in each repeating unit.

(Synthesis of polymerizable polymer containing interactive group)
(1) Synthesis of interactive group-containing polymerizable polymer 1 (Synthesis of monomer A)
In a 500 ml three-necked flask, 52.3 g of diethylene glycol monomethacrylate was added, and 250 ml of acetone was added and stirred. After adding 39.2 g of pyridine and 0.1 g of p-methoxyphenol, the mixture was cooled in an ice bath containing ice water. After the temperature of the mixture became 5 ° C. or lower, 114.9 g of 2-bromoisobutanoic acid bromide was added dropwise using a dropping funnel over 3 hours. After completion of dropping, the ice bath was removed and the mixture was further stirred for 3 hours. The reaction mixture was poured into 750 ml of water and stirred for 1 hour. The aqueous mixture was extracted three times with 500 ml of ethyl acetate using a separatory funnel. The organic layer was washed successively with 500 ml of 1M hydrochloric acid, 500 ml of saturated aqueous sodium hydrogen carbonate solution and 500 ml of saturated brine. 100 g of magnesium sulfate was added to the organic layer, dehydrated and dried, and then filtered. The solvent was distilled off under reduced pressure to obtain 75 g of monomer A (the following structure).

  Next, 80 g of N, N-dimethylacetamide was placed in a 1000 ml three-necked flask and heated to 75 ° C. under a nitrogen stream. A solution of 9.3 g of monomer A, 26.8 g of acrylic acid and 0.99 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) in 40 g of N, N-dimethylacetamide was added dropwise over 2.5 hours. After completion of dropping, the mixture was heated to 80 ° C. and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.

  To the reaction solution, 0.59 g of p-methoxyphenol was added, 800 g of N, N-dimethylacetamide was added, and the mixture was cooled in an ice bath containing ice water. After the temperature of the mixture became 5 ° C. or lower, 180.8 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was added dropwise using a dropping funnel. After completion of dropping, the ice bath was removed and the mixture was further stirred for 8 hours. A solution prepared by dissolving 114 ml of methanesulfonic acid in 49 g of water was added to the reaction solution, followed by stirring for 4 hours. After stirring, reprecipitation with water was performed, and the solid matter was collected by filtration, washed with water, and dried to obtain 10 g of an interactive group-containing polymerizable polymer 1.

(2) Synthesis of interactive group-containing polymerizable polymer 2 280 g of N, N-dimethylacetamide was placed in a 1000 ml three-necked flask and heated to 75 ° C. under a nitrogen stream. A solution of 130.1 g of 2-hydroxyethyl methacrylate, 29.27 g of methacrylic acid, 0.98 g of V-601 (manufactured by Wako Pure Chemical Industries) and 80 g of N, N-dimethylacetamide was added dropwise over 2.5 hours. After completion of dropping, the mixture was heated to 80 ° C. and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.
Add 0.43 g of ditertiary pentyl hydroquinone, 0.53 g of dibutyltin dilaurate, 26.3 g of Karenz MOI (manufactured by Showa Denko KK), 70 g of N, N-dimethylacetamide, and react at 55 ° C. for 6 hours. Went. Thereafter, 54.3 g of methanol was added to the reaction solution, and the reaction was further performed for 2 hours. After completion of the reaction, reprecipitation was carried out with water, and the solid matter was collected by filtration, washed with water and dried to obtain 23 g of an interactive group-containing polymerizable polymer 2.

(3) Synthesis of interactive group-containing polymerizable polymer 3 In a 500 ml three-necked flask, 200 g of N, N-dimethylacetamide, 30 g of polyacrylic acid (manufactured by Wako Pure Chemical, molecular weight: 25000), 2.4 g of tetraethylammonium benzyl chloride, diter 25 mg of shary pentyl hydroquinone and 27 g of the following monomer B were added and reacted at 100 ° C. for 5 hours under a nitrogen stream.

  Thereafter, 50 g of the reaction solution was taken, 11.6 mL of 4N NaOH was added in an ice bath, reprecipitation was performed with ethyl acetate, the solid was collected by filtration, washed with water, and dried to obtain the interactive group-containing polymerizable polymer 3. 3.1 g was obtained.

[Example 1]
<Polymer layer forming step>
The coating liquid 1 having the following composition was applied to the substrate 1 using a rod bar # 18 and dried. In addition, the film thickness of the obtained film was 0.8 μm.

-Composition of coating liquid 1-
・ Interactive group-containing polymerizable polymer 1 0.25 g
・ Methanol 3.0g

  Next, the substrate surface was exposed for 40 seconds using a 1.5 kW high pressure mercury lamp. Thereafter, the obtained film was washed with saturated aqueous sodium hydrogen carbonate to obtain a substrate A having a polymer layer 1 formed by surface graft polymerization of the above-mentioned interactive group-containing polymerizable polymer 1 on the substrate.

<Catalyst imparting step and metal film forming step>
The obtained substrate A was immersed in an aqueous solution of 1% by mass of silver nitrate (manufactured by Wako Pure Chemical Industries) for 5 minutes, and then washed with distilled water. Thereafter, electroless plating was performed for 20 minutes in an electroless plating bath having the following composition to form a metal film a.

-Composition of electroless plating bath-
・ 176g of distilled water
・ Copper sulfate pentahydrate 1.9g
・ EDTA ・ 2Na 5.54g
・ NaOH 1.58g
・ PEG (molecular weight 1000) 0.019 g
・ 2,2-bipyridyl 0.18mg
・ Formaldehyde aqueous solution 1.01 g

<Electroplating process>
The metal film a obtained above was further electroplated in an electroplating bath having the following composition for 40 minutes, and then subjected to the following rust prevention treatment and baked at 130 ° C. for 3 minutes, whereby the metal film 1 was formed. Formed.

-Composition of electroplating bath-
・ Copper sulfate pentahydrate 135g
・ Concentrated sulfuric acid 342g
・ HCl 0.25g
・ Copper Grime ST-901C 9mL
(Rohm and Haas Electronic Materials Co., Ltd.)
・ 234g of water

-Rust prevention treatment-
The metal film a after electroplating was immersed in a 1 wt% Entec CU-56 (Meltex Co., Ltd.) aqueous solution for 1 minute and washed with water.

<Metal pattern formation process>
A photosensitive dry film (manufactured by Fuji Photo Film Co., Ltd.) is laminated on the surface of the obtained metal film 1, and a mask film in which a desired conductor circuit pattern is drawn (the opening corresponds to the metal pattern forming region, mask The part was exposed to ultraviolet rays through a portion corresponding to a metal pattern non-formation region, and the image was printed and developed. Next, the portion of the metal film (copper thin film) where the resist was removed was etched using a ferric chloride etchant. Thereafter, the desired metal pattern 1 (conductive pattern) was formed on the substrate A by peeling off the dry film.

<Polymer layer removal process>
The obtained metal pattern 1 was immersed in a 3 mol / L NaOH aqueous solution and boiled for 1 hour, and the polymer layer 1 present in the non-formed region of the metal pattern 1 was removed.

  The metal pattern material 1 of Example 1 was obtained as described above.

[Example 2]
<Polymer layer forming step>
A coating liquid 2 having the following composition was applied to the substrate 1 using a rod bar # 18 and dried. In addition, the film thickness of the obtained film was 0.7 μm.

-Composition of coating liquid 2-
・ Interactive group-containing polymerizable polymer 2 0.25 g
・ Cyclohexanone 3.0g

  Next, the substrate surface was exposed for 40 seconds using a 1.5 kW high pressure mercury lamp. Thereafter, the obtained film was washed with saturated sodium bicarbonate water to obtain a substrate B having a polymer layer 2 formed by surface graft polymerization of the above-mentioned interactive group-containing polymerizable polymer 2 on the substrate.

<Catalyst application process, metal film formation process, electroplating process>
With respect to the obtained substrate B, a catalyst applying step, a metal film forming step, and an electroplating step were performed in the same manner as in Example 1 to form a metal film 2.

<Metal pattern formation process, polymer layer removal process>
A metal pattern formation process was performed on the obtained metal film 2 in the same manner as in Example 1 to form a metal pattern 2. Furthermore, the polymer layer removal process was performed by the same method as Example 1, and the polymer layer 2 which exists in the non-formation area | region of the metal pattern 2 was removed.

  Thus, a metal pattern material 2 of Example 2 was obtained.

[Example 3]
<Polymer layer forming step>
A coating liquid 3 having the following composition was applied to the substrate 1 using a rod bar # 18 and dried. In addition, the film thickness of the obtained film was 0.8 μm.

-Composition of coating liquid 3-
・ Interactive group-containing polymerizable polymer 3 0.25 g
・ Water 2.0g
・ Acetonitrile 1g

  Next, the substrate surface was exposed for 40 seconds using a 1.5 kW high pressure mercury lamp. Thereafter, the obtained film was washed with saturated aqueous sodium hydrogen carbonate to obtain a substrate C having a polymer layer 3 formed by surface graft polymerization of the interactive group-containing polymerizable polymer 3 on the substrate.

<Catalyst application process, metal film formation process>
Only the electroless plating process was performed on the obtained substrate C in the same manner as in Example 1 to form the metal film 3.

<Metal pattern formation process>
Photosensitive dry film (manufactured by Fuji Photo Film Co., Ltd.) is laminated on the surface of the obtained metal film, and a mask film in which a desired conductor circuit pattern is drawn (the opening corresponds to the metal pattern formation region, the mask portion (Corresponding to the region where the metal pattern is not formed) was exposed to ultraviolet light, and the image was printed and developed. Next, electroplating was performed for 20 minutes in the same manner as in Example 1. Next, the dry film is peeled off, and a portion of the metal film (copper thin film) from which the resist has been removed is flash-etched using a ferric chloride etchant, thereby forming a desired metal pattern 3 (conductive pattern). It was.

<Polymer layer removal process>
The obtained metal pattern 3 was subjected to a polymer layer removal step in the same manner as in Example 1 to remove the polymer layer 3 present in the region where the metal pattern 3 was not formed.

  As described above, a metal pattern material 3 of Example 3 was obtained.

[Example 4]
In Example 1, except that the substrate 2 was used in place of the substrate 1, the polymer layer forming step, the catalyst applying step, the metal film forming step, and the electroplating step were performed in the same manner as in Example 1, and the metal film 4 Formed. Further, after the metal pattern 4 was formed on the obtained metal film 4 in the same manner as in Example 1, the polymer layer removal process was performed.
As described above, a metal pattern material 4 of Example 4 was obtained.

[Example 5]
In Example 1, except that the substrate 3 was used instead of the substrate 1, the polymer layer forming step, the catalyst applying step, the metal film forming step, and the electroplating step were performed in the same manner as in Example 1, and the metal film 5 Formed. Further, a metal pattern forming step was performed on the obtained metal film 5 in the same manner as in Example 1 to form the metal pattern 5, and then a polymer layer removing step was performed.
As described above, a metal pattern material 5 of Example 5 was obtained.

Example 6
In Example 1, except that the substrate 4 was used instead of the substrate 1, the polymer layer forming step, the catalyst applying step, the metal film forming step, and the electroplating step were performed in the same manner as in Example 1, and the metal film 6 Formed. Further, a metal pattern forming process was performed on the obtained metal film 6 in the same manner as in Example 1 to form the metal pattern 6, and then a polymer layer removing process was performed.
As described above, a metal pattern material 6 of Example 6 was obtained.

[Example 7]
The polymer layer was removed in the polymer layer removal step in Example 1, except that the metal pattern 1 was immersed in a 1N LiAlH ₄ dehydrated ether solution and allowed to react at room temperature for 1 hour. The metal pattern material 7 of Example 7 was obtained after forming the metal pattern 7 by performing the polymer layer forming step, the catalyst applying step, the metal film forming step, the electroplating step, and the metal pattern forming step.

[Comparative Example 1]
In Example 1, the metal pattern 1 was formed on the board | substrate 1 by the method similar to Example 1 except not having performed the polymer layer removal process, and the metal pattern material 8 of the comparative example 1 was obtained.

[Comparative Example 2]
In Example 3, the metal pattern 3 was formed on the substrate 1 in the same manner as in Example 3 except that the polymer layer removal step was not performed, and the metal pattern material 9 of Comparative Example 2 was obtained.

<Evaluation>
1. Evaluation of ion migration resistance In each of the metal pattern materials 1 to 7 of the example and the metal pattern materials 8 and 9 of the comparative example, the metal pattern region is formed into the shape of a comb-shaped electrode (conductor) defined in IPC-SM-840. A width: 100 μm, an interval between conductors: 100 μm, an overlap margin: 15.75 mm, see FIG.
In the evaluation test, first, the metal pattern materials 1 to 9 are set inside a constant temperature and humidity test tank, a voltage is applied from the outside by a standard voltage generator, and after 50 hours, the metal pattern materials 1 to 9 are taken out from the constant temperature and humidity test tank. The presence or absence of ion migration was observed at. The test environmental conditions were 80 ° C. and 90% R.D. H. The applied voltage was 49V.
Further, for the metal pattern materials 1 to 9, the line insulation resistance during the evaluation test is constantly monitored using a migration evaluation system (ESPEC migration evaluation system AMI), and the line insulation resistance is 10 ⁵ during the test. The case where Ω or more was maintained was evaluated as “◯”, and the case where the insulation resistance between lines was 10 ⁵ Ω or less was evaluated as “x”. The results are shown in Table 1.

2. Evaluation of conductivity of metal pattern region For each of the metal pattern materials 1 to 7 of the example and the metal pattern materials 8 and 9 of the comparative example, the surface resistance of the metal pattern region is measured by a resistivity meter (Loresta-EP, model number MCP- T360, manufactured by Mitsubishi Chemical Corporation). The measurement results are shown in Table 1.

3. Evaluation of adhesion between the metal pattern region and the substrate Each of the metal pattern materials 1 to 7 of the example and the metal pattern materials 8 and 9 of the comparative example was evaluated by performing a cross-cut test in accordance with JIS K5600. The results are shown in Table 1.

As shown in Table 1, the metal pattern materials 1 to 7 obtained by the methods of Examples 1 to 7 are all subjected to an evaluation test under conditions of high temperature and high humidity. It can be seen that no migration was observed and the high insulation resistance between lines was maintained. Moreover, it turns out that a metal pattern formation area is high electroconductivity and is excellent in adhesiveness with a board | substrate.
On the other hand, the metal pattern materials 8 and 9 of Comparative Examples 1 and 2 that were not subjected to the polymer layer removal step were excellent in the conductivity of the metal pattern formation region and the adhesion to the substrate, but migration occurred. It can be seen that the insulation resistance between lines is reduced.

It is a figure which shows the shape of the comb electrode prescribed | regulated to IPC-SM-840.

Claims (8)

(A) a polymer layer forming step of forming a polymer layer on a substrate by forming a graft polymer having a functional group that directly binds to the surface of the substrate and interacts with the electroless plating catalyst or a precursor thereof;
(B) a catalyst application step of applying an electroless plating catalyst or a precursor thereof to the polymer layer;
(C) a metal film forming step of forming a metal film on the entire surface of the polymer layer by performing electroless plating;
(D) a metal pattern forming step of forming a metal pattern by removing a part of the metal film, and
(E) a polymer layer removing step for removing the polymer layer present in the non-formation region of the metal pattern;
A method for producing a metal pattern material, comprising:   The method for producing a metal pattern material according to claim 1, wherein the polymer layer removing step is performed by hydrolysis.   2. The substrate according to claim 1, wherein the substrate is a substrate made of an insulating resin having a dielectric loss tangent at 1 GHz of 0.01 or less, or a substrate having a layer made of the insulating resin on a base material. Item 3. A method for producing a metal pattern material according to Item 2.   The substrate is a substrate made of an insulating resin having a dielectric constant of 3.5 or less at 1 GHz, or a substrate having a layer made of the insulating resin on a base material. Item 4. The method for producing a metal pattern material according to any one of Items 3 to 3.   In the polymer layer forming step (a), the substrate is contacted with a polymer having a functional group and a polymerizable group that interacts with an electroless plating catalyst or a precursor thereof, and then the substrate is applied with energy. The method for producing a metal pattern material according to any one of claims 1 to 4, which is a step of directly chemically bonding the polymer to the entire surface.   The (a) polymer layer forming step includes (a-1) a step of producing a substrate on which a layer expressing the polymerization initiating ability is formed, and (a-2) expressing the polymerization initiating ability. The method further comprising the step of directly chemically bonding a polymer having a functional group and a polymerizable group that interacts with the electroless plating catalyst or its precursor on the substrate on which the layer is formed. 5. The method for producing a metal pattern material according to any one of 4 above.   In the step (a-2), a polymer having a functional group and a polymerizable group that interacts with the electroless plating catalyst or its precursor is brought into contact with the substrate on which the layer expressing the polymerization initiating ability is formed. The method for producing a metal pattern material according to claim 6, which is a step of directly chemically bonding the polymer to the entire substrate surface by applying energy.   The substrate has a metal pattern having a polymer layer made of a graft polymer directly chemically bonded to the substrate and a plating layer formed inside and on the polymer layer, and the non-formation region of the metal pattern is the polymer A metal pattern material characterized by being an area where no layer exists.

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