JP2008274390A - Process for producing metal-film-coated substrate, metal-film-coated substrate, process for producing metallic-pattern material, and metallic-pattern material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal-film-coated substrate which has a metal film having excellent adhesion to the substrate and which has a small dependence on temperature and humidity, and a process for producing the substrate; and also to provide a metallic-pattern material which has a metallic pattern having excellent adhesion to the substrate, a small dependence on temperature and humidity, and excellent insulation reliability in the regions not covered by the metallic pattern, and a process for producing the material. <P>SOLUTION: The process for producing a metal-film-coated substrate is characterized by including: a step (a1) in which a polymer layer is formed on a substrate, the polymer layer being made of a polymer which has a non-dissociable functional group interacting with a plating catalyst or a precursor therefor and capable of multidentate coordination and which is directly and chemically bonded to the substrate; a step (a2) in which a plating catalyst or precursor therefor capable of multidentate coordination is imparted to the polymer layer; a step (a3) in which a metal different from the plating catalyst or precursor therefor capable of multidentate coordination is incorporated into the polymer layer, and a step (a4) in which the plating catalyst or precursor therefor capable of multidentate coordination is plated. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a substrate with a metal film and a metal pattern material, and more particularly to a method for producing a substrate with a metal film and a metal pattern material that are useful as a metal wiring board and a printed 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.
As a method for producing such a metal pattern material, a “subtractive method” is mainly used. In this subtractive method, a photosensitive layer that is exposed by irradiation with actinic rays is provided on a metal film formed on the surface of the substrate, the photosensitive layer is exposed imagewise, and then developed to form a resist image. In this method, the metal film is etched to form a metal pattern, and finally the resist is removed.

  In the metal pattern obtained by this method, the adhesion between the substrate and the metal film 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, according to this method, when the graft polymer has a polar group, in particular, a dissociable group, moisture absorption or desorption is likely to occur due to changes in temperature or humidity, resulting in deformation of the formed metal film or substrate. Had the problem of end up.
In addition, when the metal pattern obtained using this method is used as the wiring of a metal wiring board, a graft polymer having a polar group and a dissociative group remains at the interface portion of the board, and retains moisture, ions, etc. Therefore, there are concerns about temperature / humidity dependence, resistance to ion migration between wires, and changes in shape. In particular, when applied to fine wiring such as printed wiring boards, high insulation between wirings (metal patterns) is required, and there is a demand for further improvement in insulation reliability between wirings. It is.
Advanced Materials 2000 No. 20 1481-1494

An object of the present invention made in consideration of the above-mentioned conventional technical problems is to provide a metal film-coated substrate having a metal film having excellent adhesion to the substrate and having low temperature / humidity dependency, and a method for manufacturing the same. It is to provide.
In addition, the second object of the present invention is a metal pattern material having a metal pattern with excellent adhesion to the substrate, low temperature / humidity dependency, and excellent insulation reliability in the non-formation region of the metal pattern, And providing a manufacturing method thereof.

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> (a1) A polymer having a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof on a substrate, and a polymer that is directly chemically bonded to the substrate. Forming a layer; (a2) providing a plating catalyst capable of multidentate coordination or a precursor thereof to the polymer layer; and (a3) a plating catalyst capable of multidentate coordination to the polymer layer or the same. Production of a substrate with a metal film, comprising: a step of containing a metal different from the precursor; and (a4) a step of plating the plating catalyst capable of multidentate coordination or a precursor thereof. Is the method.

  <2> The non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor is a nitrogen-containing functional group, an oxygen-containing functional group, or a sulfur-containing functional group. The method for producing a substrate with a metal film according to <1>.

  <3> The non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor is a nitrogen-containing functional group, according to <1> or <2> It is a manufacturing method of a board | substrate with a metal film.

  <4> The method for producing a substrate with a metal film according to any one of <1> to <3>, wherein the plating catalyst capable of multidentate coordination or a precursor thereof is palladium or palladium ions. It is.

  <5> The metal different from the plating catalyst or precursor thereof capable of multidentate coordination is silver, copper, nickel, cobalt, tin, chromium, or zinc. <1> to <4> The method for producing a substrate with a metal film according to any one of the above.

  <6> A substrate with a metal film obtained by the method for producing a substrate with a metal film according to any one of <1> to <5>.

  <7> (b1) A polymer comprising a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof on a substrate, and a polymer that is directly chemically bonded to the substrate. Forming a layer; (b2) providing a plating catalyst capable of multidentate coordination or a precursor thereof to the polymer layer; and (b3) a plating catalyst capable of multidentate coordination to the polymer layer or the same. A step of containing a metal different from the precursor, (b4) a step of plating the plating catalyst capable of multidentate coordination or its precursor, and (b5) etching the formed plating film into a pattern A process for producing a metal pattern material.

  <8> (c1) A polymer comprising a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof on a substrate, and a polymer that is directly chemically bonded to the substrate. A step of forming a layer in a pattern, (c2) a step of applying a plating catalyst or precursor thereof capable of multidentate coordination to the polymer layer, and (c3) plating capable of multidentate coordination of the polymer layer. A metal pattern material comprising: a step of containing a metal different from the catalyst or its precursor; and (c4) a step of plating the plating catalyst capable of multidentate coordination or a precursor thereof. This is a manufacturing method.

  <9> The non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor is a nitrogen-containing functional group, an oxygen-containing functional group, or a sulfur-containing functional group. <7> or <8> The method for producing a metal pattern material according to <8>.

  <10> Any one of <7> to <9>, wherein the non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or a precursor thereof is a nitrogen-containing functional group 1. A method for producing a metal pattern material according to 1.

  <11> The method for producing a metal pattern material according to any one of <7> to <10>, wherein the multidentate plating catalyst or a precursor thereof is palladium or palladium ions. is there.

  <12> The metal different from the multidentate plating catalyst or precursor thereof is silver, copper, nickel, cobalt, tin, chromium, or zinc <7> to <11> The method for producing a metal pattern material according to any one of the above.

  <13> A metal pattern material obtained by the method for producing a metal pattern material according to any one of <7> to <12>.

According to the present invention, it is possible to provide a substrate with a metal film that has a metal film excellent in adhesion to the substrate and has low temperature / humidity dependency, and a method for manufacturing the same. It is in.
Further, according to the present invention, a metal pattern material having a metal pattern with excellent adhesion to the substrate, low temperature / humidity dependency, and excellent insulation reliability in a non-formation region of the metal pattern, and its production A method can be provided.

Hereinafter, the present invention will be described in detail. First, the manufacturing method of the board | substrate with a metal film of this invention is demonstrated.
<Method for producing substrate with metal film>
The method for producing a substrate with a metal film of the present invention comprises (a1) a substrate having a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof, and the substrate. Forming a polymer layer comprising a polymer directly chemically bonded to the polymer layer, (a2) providing a plating catalyst or precursor thereof capable of multidentate coordination to the polymer layer, and (a3) applying a multi-layer to the polymer layer. A step of containing a metal different from a plating catalyst capable of coordinating coordination or a precursor thereof, and (a4) a step of plating the plating catalyst capable of multidentate coordination or a precursor thereof. Features.
Hereinafter, each step will be described.

[Step (a1)]
In the step (a1), a non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor on the substrate (hereinafter simply referred to as “interactive group”). And a polymer layer made of a polymer that is directly chemically bonded to the substrate.

The step (a1) includes: (a1-1) a step of producing a substrate on which a polymerization initiator layer containing a polymerization initiator is formed on a substrate; and (a1-2) an interactive group on the polymerization initiator layer. And a step of forming a polymer layer made of a polymer that is directly chemically bonded to the polymerization initiation layer.
In the step (a1-2), after the polymer having a polymerizable group and an interactive group is brought into contact with the polymerization initiation layer, energy is applied to the entire substrate surface (polymerization initiation layer). It is preferably a step of directly chemically bonding the polymer to the entire surface).

(Surface graft)
Formation of the polymer layer on the substrate uses a general method called surface graft polymerization. Graft polymerization is a method of synthesizing a graft (grafting) polymer by providing an active species on a polymer compound chain, thereby further polymerizing another monomer that initiates polymerization. In particular, when a polymer compound that gives active species forms a solid surface, this is called surface graft polymerization.

Any known method described in the literature can be used as the surface graft polymerization method applied to the present invention. For example, New Polymer Experimental Science 10, edited by Polymer Society, 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, the methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used.

When forming the polymer layer in the present invention, in addition to the surface graft method described above, a reactive functional group such as a trialkoxysilyl group, an isocyanate group, an amino group, a hydroxyl group, or a carboxyl group is attached to the end of the polymer compound chain. It is also possible to apply a method in which these are bonded by a coupling reaction between this and a functional group present on the substrate surface.
Among these methods, from the viewpoint of generating more graft polymers, it is preferable to form a polymer layer using a photograft polymerization method.

〔substrate〕
The “substrate” in the present invention is a function capable of forming a state in which a polymer having a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof is directly chemically bonded. The substrate itself may have such surface characteristics, and an intermediate layer (for example, a polymerization initiation layer described later) is separately provided on the base material. It may have such characteristics.

(Base material, substrate)
The substrate used in the present invention is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), metal plate (for example, , Aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, Polyimide, epoxy, bismaleimide resin, polyphenylene oxide, liquid crystal polymer, polytetrafluoroethylene, etc.), and paper or plastic film laminated or vapor-deposited with the above metals . As a base material used for this invention, an epoxy resin or a polyimide resin is preferable.
In addition, the surface of these base materials has a function capable of forming a state in which a polymer having a non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor is directly chemically bonded. If it is, the base material itself may be used as the substrate.

  As the substrate in the present invention, a substrate containing polyimide having a polymerization initiation site described in paragraphs [0028] to [0088] of JP-A-2005-281350 in the skeleton can also be used.

  Moreover, the substrate with a metal film (the substrate with a metal film of the present invention) obtained by the method for producing a substrate with a metal film of the present invention is applied to a semiconductor package, various electric wiring substrates, etc. by patterning by etching. be able to. When used in such applications, the following substrate containing an insulating resin, specifically, a substrate made of an insulating resin or a substrate having a layer made of an insulating resin on a base material is used. It is preferable.

When obtaining a substrate made of an insulating resin or a layer made of an insulating resin, a known insulating resin composition is used. In addition to the main resin, various additives can be used in combination with the insulating resin composition depending on the purpose. For example, a means such as adding a polyfunctional acrylate monomer for the purpose of increasing the strength of the insulating layer, or adding inorganic or organic particles for the purpose of increasing the strength of the insulating layer and improving electrical characteristics, etc. It can also be taken.
In addition, the “insulating resin” in the present invention means a resin having an insulating property that can be used for a known insulating film or insulating layer, and is not a perfect insulator. In addition, any resin having insulating properties according to the purpose can be applied to the present invention.

Specific examples of the insulating resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof. Examples of the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, and a bismaleimide. Examples thereof include resins, polyolefin resins, isocyanate resins and the like.
Examples of the epoxy resin include cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, dicyclo Examples thereof include pentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, and alicyclic epoxy resins. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.
Examples of the polyolefin resin include polyethylene, polystyrene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, cycloolefin resin, and copolymers of these resins.

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

  The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. This is performed for the purpose of compensating for each defect and producing a superior effect. For example, thermoplastic resins such as polyphenylene ether (PPE) have a low resistance to heat, and are therefore alloyed with thermosetting resins. For example, it is used for alloying PPE with epoxy and triallyl isocyanate, or alloying PPE resin into which a polymerizable functional group is introduced and other thermosetting resins. Cyanate ester is a resin having the most excellent dielectric properties among thermosetting, but it is rarely used alone, and is used as a modified resin such as epoxy resin, maleimide resin, and thermoplastic resin. Details thereof are described in "Electronic Technology" 2002/9, P35. Moreover, what contains an epoxy resin and / or a phenol resin as a thermosetting resin, and contains a phenoxy resin and / or polyether sulfone (PES) as a thermoplastic resin is also used in order to improve a dielectric characteristic.

  The insulating resin composition may contain a compound having a polymerizable double bond in order to promote crosslinking, specifically, an acrylate or methacrylate compound, and particularly a polyfunctional one. preferable. In addition, as a compound having a polymerizable double bond, methacrylic acid or acrylic acid is used for a thermosetting resin or a thermoplastic resin, for example, an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, or the like. Alternatively, a resin obtained by subjecting a part of the resin to (meth) acrylation reaction may be used.

  The insulating resin composition according to the present invention includes a composite of a resin and other components (in order to enhance the mechanical strength, heat resistance, weather resistance, flame resistance, water resistance, electrical characteristics, etc.) of the resin film. Composite materials) can also be used. Examples of the material used for the composite include paper, glass fiber, silica particles, phenol resin, polyimide resin, bismaleimide triazine resin, fluorine resin, polyphenylene oxide resin, and the like.

Further, this insulating resin composition may be filled with a filler used for general wiring board resin materials as necessary, for example, inorganic fillers such as silica, alumina, clay, talc, aluminum hydroxide, calcium carbonate, and cured epoxy. You may mix | blend 1 type, or 2 or more types of organic fillers, such as resin, crosslinked benzoguanamine resin, and a crosslinked acrylic polymer.
Furthermore, the insulating resin composition may contain one or two various additives such as a colorant, a flame retardant, an adhesion imparting agent, a silane coupling agent, an antioxidant, and an ultraviolet absorber as necessary. More than seeds may be added.

  When these materials are added to the insulating resin composition, it is preferable to add them in the range of 1 to 200% by mass, and more preferably in the range of 10 to 80% by mass with respect to the resin. Is done. When this addition amount is less than 1% by mass, there is no effect of enhancing the above properties, and when it exceeds 200% by mass, properties such as strength specific to the resin are lowered.

Specifically, the substrate used in such applications is a substrate made of an insulating resin having a dielectric constant (relative dielectric constant) at 1 GHz of 3.5 or less, or made of the insulating resin. A substrate having a layer on a substrate is preferred. Moreover, it is preferable that it is a board | substrate which consists of insulating resin whose dielectric loss tangent in 1 GHz is 0.01 or less, or a board | substrate which has the layer which consists of this insulating resin on a base material.
The dielectric constant and dielectric loss tangent of the insulating resin can be measured by a conventional method. For example, the cavity resonator perturbation method (for example, εr, tanδ measuring instrument for ultra-thin sheet, manufactured by Keycom Corporation) based on the method described in “18th Annual Conference of Electronics Packaging Society”, p189, 2004. ).
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 insulating resins having a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.01 or less include liquid crystal polymers, polyimide resins, fluororesins, polyphenylene ether resins, cyanate ester resins, and bis (bisphenylene) ethane resins. Furthermore, those modified resins are also included.

  The substrate applied to the method for producing a substrate with a metal film of the present invention preferably has a surface irregularity of 500 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, and most preferably 20 nm or less. The smaller the surface irregularity of this substrate (the surface irregularity of the layer when an intermediate layer or polymerization initiation layer is provided), the smaller the electric power during high-frequency power transmission when the obtained metal film-coated substrate is applied to wiring, etc. Loss is reduced, which is preferable.

In the present invention, when a surface graft polymerization method in which an active species is given to the substrate surface and a graft polymer is generated from the active species is used, a polymerization initiator layer containing a polymerization initiator is formed on the base material when the graft polymer is formed. It is preferable to use the formed substrate. By using this substrate, active sites can be efficiently generated and more graft polymers can be generated.
Hereinafter, the polymerization initiation layer in the present invention will be described.

(Polymerization initiation layer)
Examples of the polymerization initiation layer in the present invention include a layer containing a polymer compound and a polymerization initiator, and a layer containing a polymerizable compound and a polymerization initiator.
The polymerization initiating layer in the present invention can be formed by dissolving necessary components in a soluble solvent, providing on the surface of the substrate by a method such as coating, and hardening by heating or light irradiation.

  The compound used for the polymerization initiation layer in the present invention is not particularly limited as long as it has good adhesion to the substrate and generates active species by applying energy such as actinic ray irradiation. it can. Specifically, a mixture of a polyfunctional monomer or a hydrophobic polymer having a polymerizable group in the molecule and a polymerization initiator can be used.

Specific examples of the hydrophobic polymer having a polymerizable group in the molecule include diene homopolymers such as polybutadiene, polyisoprene and polypentadiene, allyl (meth) acrylate, 2-allyloxyethyl. Homopolymers of allyl group-containing monomers such as methacrylic soot;
Binary or multi-component copolymers such as styrene, (meth) acrylic acid ester, (meth) acrylonitrile and the like containing diene monomers such as butadiene, isoprene and pentadiene or allyl group-containing monomers as constituent units;
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 these polymerizable compounds is preferably in the range of 10 to 100% by mass, particularly preferably in the range of 10 to 80% by mass in terms of solid content in the polymerizable layer.

The polymerization initiation layer contains a polymerization initiator for expressing polymerization initiation ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, etc. that can exhibit polymerization initiation ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Depending on the purpose, it can be appropriately selected and used. Among these, use of photopolymerization is preferable from the viewpoint of production suitability, and therefore, it is preferable to use a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it is active with respect to irradiated actinic rays and can be subjected to surface graft polymerization from the polymerization initiation layer containing the photopolymerization initiator, and examples thereof include radical polymerization initiators and anionic polymerizations. An initiator, a cationic polymerization initiator, and the like can be used, but a radical polymerization initiator is preferable from the viewpoint of reactivity.

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

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 polymerization initiating layer is formed on the substrate is, in terms of the expression after sufficient polymerization initiating ability and maintaining the film properties to prevent film peeling, in terms of the mass after drying, being 0. 1 to 20 g / m ² is preferable, and 0.5 to 15 g / m ² is more preferable.

In the present invention, as described above, the composition for forming the polymerization initiation layer is disposed on the base material by coating or the like, and the film is formed by removing the solvent to form the polymerization initiation layer. Sometimes, it is preferable to harden by heating and / or 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 after the polymerization polymer is formed on the polymerization initiation layer, the polymerization initiation layer is removed. This is preferable because it is possible to effectively suppress such a situation.
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.

  The light irradiation performed as desired after heat-drying can use the light source used for the production | generation reaction of the graft polymer mentioned later. In the subsequent graft polymer generation step, the polymerization initiator existing in the polymerization start layer cures the polymerizable compound from the viewpoint of not inhibiting the active point of the polymerization start layer generated by energy application and the generation of the graft polymer. Even when radical polymerization is performed, it is preferable to irradiate with light so that it is not completely consumed. About light irradiation time, although it changes with the intensity | strength of a light source, generally it is preferable within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent cleaning is 80% or less and the initiator remaining rate after pre-curing is 1% or more.

In addition to the polymerization initiating layer containing the polymerizable compound and the polymerization initiator, a polymerization initiating layer using a polymer in which a polymerization initiating group described in JP-A-2004-161995 is pendant on a side chain is also preferable. Specifically, this polymer is a polymer having a functional group (polymerization initiating group) having a polymerization initiating ability in the side chain and a crosslinkable group (hereinafter referred to as a polymerization initiating polymer). It is possible to form a polymerization initiating layer having a polymerization initiating group bonded to and having a polymer chain immobilized by a crosslinking reaction.
The polymerization initiating layer thus formed is also suitable as the polymerization initiating layer of the present application.

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

-Formation of polymerization initiation layer-
The polymerization initiating layer using the polymerization initiating polymer in the present invention is prepared by dissolving the above-mentioned polymerization initiating polymer in an appropriate solvent, preparing a coating solution, placing the coating solution on a substrate by coating, and the like. The film is formed by removing and proceeding with the crosslinking reaction. That is, the polymerization initiating polymer is fixed by the progress of the crosslinking reaction. The immobilization by the crosslinking reaction includes a method using a self-condensation reaction of a polymerization initiating polymer and a method using a crosslinking agent in combination, and it is preferable to use a crosslinking agent. As a method of using the self-condensation reaction of the polymerization initiating polymer, for example, when the crosslinkable group is —NCO, the property that the self-condensation reaction proceeds by applying heat is used. 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 polymerization initiating polymer include (crosslinkable group, crosslinker) = (— COOH, polyvalent amine), (—COOH, polyvalent aziridine), (—COOH, many 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 anhydrides). Among these, (functional group, cross-linking agent) = (— OH, polyvalent isocyanate) is a more preferable combination in that a urethane bond is formed after the cross-linking and a high-strength cross-linking can be formed.

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

  Such a crosslinking agent is added to the coating solution containing the above-mentioned 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.

  Further, the amount of the crosslinking agent added in the coating solution varies depending on the amount of the crosslinkable group introduced into the polymerization initiating polymer. However, the degree of crosslinking and the influence on the polymerization reaction due to the residual unreacted crosslinking component remain. In view of the above, 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. Further preferred.

Moreover, the solvent used when apply | coating a polymerization start layer will not be restrict | limited especially if the above-mentioned 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 initiating layer using the polymerization initiating polymer is preferably 0.1 to 20 g / m ² in terms of weight after drying from the viewpoint of the ability to initiate surface graft polymerization and film properties, 15 g / m ² is preferred.

Furthermore, in the present invention, when a substrate having a layer made of an insulating resin as described above is used on the base material, a known polymerization initiator is contained in the layer made of the insulating resin to provide an insulating property. The polymerization initiation layer is preferably used. The polymerization initiator contained in this insulating polymerization initiator layer is not particularly limited. For example, the above-described thermal polymerization initiator, photopolymerization initiator (radical polymerization initiator, anionic polymerization initiator, cationic polymerization start) Agent), a polymer compound having an active carbonyl group in the side chain described in JP-A-9-77891 and JP-A-10-45927, and further, a functional group having a polymerization initiating ability and a crosslinkable group in the side chain. The polymer (polymerization initiating polymer) etc. which have can be used.
In general, the amount of the polymerization initiator contained in the insulating polymerization start layer is preferably about 0.1 to 50% by mass in terms of solid content in the insulating layer, and is preferably 1.0 to 30.0. More preferably, it is about mass%.

(Generation of graft polymer)
As described above, the graft polymer is generated in the step (a1) by using a coupling reaction between the functional group present on the substrate surface and the reactive functional group of the polymer compound at the terminal or side chain. Alternatively, photograft polymerization can be used.
In the present invention, a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof on the polymerization initiation layer using a substrate having a polymerization initiation layer formed on a substrate. An embodiment [(a1-2) step] in which a polymer layer comprising a polymer having an (interactive group) and directly chemically bonded to the polymerization initiation layer is preferable. More preferably, after the polymer having a polymerizable group and an interactive group is brought into contact with the polymerization initiation layer, the polymer is directly applied to the entire substrate surface (the entire polymerization initiation layer surface) by applying energy. This is a mode of chemical bonding. That is, a compound having a polymerizable group and an interactive group is directly bonded with an active species generated on the surface of the polymerization initiation layer while the composition containing the compound is brought into contact with the surface of the polymerization initiation layer. It is.

  The contact may be performed by immersing the substrate on which the polymerization initiating layer is formed in a liquid composition containing a compound having a polymerizable group and an interactive group. From the viewpoint, as described later, a layer mainly composed of a composition containing a compound having a polymerizable group and an interactive group may be formed on the substrate surface (polymerization initiation layer surface) by a coating method. .

In the present invention, a non-dissociative functional group capable of multidentate coordination (interaction) that forms an interaction with a polymerizable group and a plating catalyst or a precursor thereof, which is used when a graft polymer is formed by a surface graft polymerization method. The compound having a functional group) will be described.
In the present invention, an interactive group (non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof) in a compound having a polymerizable group and an interactive group is a functional group. This is a functional group in which a group does not generate a proton by dissociation and can be coordinated by interaction with a plating catalyst or its precursor by intermolecular force.
This interactive group is preferably a nitrogen-containing functional group, an oxygen-containing functional group, a sulfur-containing functional group, and the like. Specifically, an imide group, a pyridine group, a tertiary amino group, an ammonium group, a pyrrolidone Group, amidino group, group containing triazine ring structure, group containing isocyanuric structure, nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyanate group (R—O—CN) and other nitrogen-containing functions Groups, ether groups, carbonyl groups, ester groups, groups containing N-oxide structures, groups containing S-oxide structures, oxygen-containing functional groups such as groups containing N-hydroxy structures, thioether groups, thioxy groups, sulfoxide groups, Sulfur-containing functional groups such as sulfone group, sulfite group, group containing sulfoxyimine structure, group containing sulfoxynium salt structure, group containing sulfonate structure, etc. Phosphorus-containing functional group such as Sufin group, chlorine, a group containing a halogen atom such as bromine, and unsaturated ethylenic group and the like. In addition, an imidazole group, a urea group, or a thiourea group may be used as long as it is non-dissociative due to a relationship with an adjacent atom or atomic group.
Among them, since it has high polarity and high adsorption ability to a plating catalyst or the like, it is represented by an ether group (more specifically, —O— (CH ₂ ) _n —O— (n is an integer of 1 to 5). Structures containing a pyridyl group, a cyano group, an ether group, and a thioether group are particularly preferred.
Although this functional group has a function of forming an interaction with the plating catalyst or its precursor, it does not have a dissociable polar group (hydrophilic group), so a polymer made of a graft polymer having this functional group The layer has a low temperature / humidity dependency.

In the present invention, the compound having a polymerizable group and an interactive group may be in the form of a monomer, a macromonomer, or a polymer. Among these, from the viewpoint of the formability of the polymer layer and the ease of control, the polymer It is preferable to use (polymer having a polymerizable group and an interactive group).
Examples of the polymer having a polymerizable group and an interactive group include homopolymers and copolymers obtained using a monomer having an interactive group, such as a vinyl group, an allyl group, and a (meth) acryl group. A polymer having an ethylene addition polymerizable unsaturated group (polymerizable group) introduced therein is preferable, and the polymer having a polymerizable group and an interactive group has a polymerizable group at least at the main chain terminal or side chain. And those having a polymerizable group in the side chain are preferred.
In addition, the polymerizable group in the present invention is a functional group in which compounds having a polymerizable group and an interactive group are bonded to each other, or a compound having a polymerizable group and an interactive group is bonded to a substrate by energy application. In addition to the above ethylene addition polymerizable unsaturated groups, vinyl groups, vinyloxy groups, allyl groups, acryloyl groups, methacryloyl groups, oxetane groups, epoxy groups, isocyanate groups, functional groups containing active hydrogen, active groups in azo compounds, etc. Is mentioned.

  Examples of the monomer having an interactive group used in obtaining the polymer having the polymerizable group and the interactive group include vinylpyridines and N-vinylpyrrolidone, and these are used alone. Two or more kinds may be used in combination.

  In the polymer having a polymerizable group and an interactive group, the unit derived from the monomer having an interactive group is a polymerizable group and an interactive group from the viewpoint of forming an interaction with the plating catalyst or its precursor. It is preferable to contain in the range of 50-95 mol% in the polymer which has this, and it is more preferable to contain in the range of 40-80 mol%.

  Moreover, when obtaining the polymer which has a polymeric group and an interactive group, you may synthesize | combine using another monomer other than the monomer which has the said interactive group. As the other monomer, a general polymerizable monomer may be used, and examples thereof include a diene monomer and an acrylic monomer.

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

  As the monomer having an interactive group used for the synthesis of a polymer having a polymerizable group and an interactive group, the same monomers as those having the above interactive group can be used. A monomer may be used individually by 1 type and may use 2 or more types together.

Examples of the monomer having a polymerizable group to be copolymerized with a monomer having an interactive group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Examples of the monomer having a double bond precursor include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate, 2- (3-bromo-1-oxopropoxy) ethyl methacrylate, and the like.

  Furthermore, the polymerizability used for introducing an unsaturated group by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group, and an epoxy group in a polymer having an interactive group. Examples of the monomer having a group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

The average molecular weight of the polymer having a polymerizable group and an interactive group in the present invention is preferably from 1,000 to 700,000, more preferably from 2,000 to 300,000.
Moreover, as a polymerization degree of the polymer which has a polymeric group and an interaction group in this invention, it is preferable to use a thing more than a 10-mer, More preferably, it is a thing more than a 20-mer. Moreover, 7000-mer or less is preferable, 3000-mer or less is more preferable, 2000-mer or less is still more preferable, 1000-mer or less is especially preferable.

  Hereinafter, specific examples of the polymer having a polymerizable group and an interactive group that are preferably used in the present invention will be shown, but the present invention is not limited thereto.

  The compound having a polymerizable group and an interactive group in the present invention is polar insofar as the water absorption of the formed polymer layer is within the range not impairing the effects of the present invention, in addition to the polymerizable group and the interactive group. It may have a group. By having a polar group, for example, when a protective layer is provided after a metal film is formed by a process described later, the adhesion can be improved in the contact region between the polymer layer and the protective layer. .

The solvent used for the composition containing a compound having a polymerizable group and an interactive group, such as a polymer having a polymerizable group and an interactive group, is the main component of the composition, the polymerizable group and the interaction There is no particular limitation as long as a compound having a functional group can be dissolved. A surfactant may be further added to the solvent.
Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone and cyclohexanone, amides such as formamide and dimethylacetamide. System solvents, and the like.

Moreover, in this invention, when apply | coating the composition containing the compound which has a polymeric group and an interactive group on a board | substrate or a polymerization start layer, the solvent absorption rate of a board | substrate or a polymerization start layer is 5-25%. The solvent can be selected. This solvent absorption rate can be determined from the change in mass when the substrate or the substrate on which the polymerization initiation layer is formed is immersed in the solvent and pulled up after 1000 minutes.
In addition, when a composition containing a compound having a polymerizable group and an interactive group is applied on a substrate or a polymerization initiation layer, a solvent in which the swelling rate of the substrate or the polymerization initiation layer is 10 to 45% is selected. May be. This swelling ratio can be determined from the change in thickness when the substrate or the substrate on which the polymerization initiation layer is formed is immersed in a solvent and pulled up after 1000 minutes.

  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.

  A polymerization inhibitor may be added to the composition containing a compound having a polymerizable group and an interactive group, if necessary. Examples of the polymerization inhibitor that can be used include hydroquinones such as hydroquinone, ditertiary butyl hydroquinone and 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, phenols such as p-methoxyphenol and phenol, Nitrosamines such as benzoquinones, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy free radical), free radicals such as 4-hydroxy TEMPO, phenothiazines, N-nitrosophenylhydroxyamine, and aluminum salts thereof Catechols can be used.

In addition, a curing agent and / or a curing accelerator can be added to the composition containing a compound having a polymerizable group and an interactive group, as necessary, in order to advance curing of the polymerization initiation layer. . For example, as a curing agent and / or curing accelerator when an epoxy compound is contained in the polymerization initiation layer, in the polyaddition type, aliphatic polyamine, alicyclic polyamine, aromatic polyamine, polyamide, acid anhydride, phenol, phenol Examples of catalyst types such as novolak, polymercaptan, compounds having two or more active hydrogens include aliphatic tertiary amines, aromatic tertiary amines, imidazole compounds, and Lewis acid complexes.
Also, those that start curing by heat, light, moisture, pressure, acid, base, etc. include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyamideamine, mensendiamine, isophoronediamine, N-amino. Ethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4 -Aminocyclohexyl) methane, m-xylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, dicyandiamide, adipic dihydrazide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylteto Hydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate), Methylcyclohexenetetracarboxylic anhydride, trimellitic anhydride, polyazeline acid anhydride, phenol novolak, xylylene novolak, bis A novolak, triphenylmethane novolak, biphenyl novolak, dicyclopentadiene phenol novolak, terpene phenol novolak, polymercaptan Polysulfide, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol-tri-2-ethylhexene Lurate, benzyldimethylamine, 2- (dimethylaminomethyl) phenol 2-methylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl- 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1))-ethyl S-triazine, BF ₃ monoethylamine complex, Lewis acid complex, organic acid Examples include hydrazide, diaminomaleonitrile, melamine derivatives, imidazole derivatives, polyamine salts, amine imide compounds, aromatic diazonium salts, diallyl iodonium salts, triallyl sulfonium salts, triallyl selenium salts, ketimine compounds, and the like.

  These curing agents and / or effect accelerators may be added up to about 0 to 50% by mass of the remaining non-volatile components from which the solvent has been removed from the viewpoints of solution applicability, adhesion to substrates and plating films, and the like. preferable. Moreover, you may add a hardening | curing agent and / or a hardening accelerator to a polymerization start layer, In that case, it is preferable to satisfy | fill the said range with the quantity added to the polymerization start layer, and the total amount added in the polymer layer.

  Furthermore, plasticizers, rubber components (for example, CTBN), flame retardants (for example, phosphorus flame retardants), diluents and thixotropic agents, pigments, antifoaming agents, leveling agents, couplings An agent or the like may be added. Moreover, you may add these additives to a polymerization start layer as needed.

By using a composition in which a compound having these polymerizable group and interactive group and various additives are appropriately mixed, the physical properties of the formed polymer layer, for example, thermal expansion coefficient, glass transition temperature, Young's modulus , Poisson's ratio, breaking stress, yield stress, pyrolysis temperature, etc. can be set optimally. In particular, it is preferable that the breaking stress, yield stress, and thermal decomposition temperature be higher.
The obtained polymer layer can be measured for thermal durability by a temperature cycle test, a thermal aging test, a reflow test, and the like. For example, with respect to thermal decomposition, a mass loss when exposed to an environment of 200 ° C. for 1 hour is 20 % Or less, it can be evaluated that it has sufficient heat durability.

When a composition containing a compound having a polymerizable group and an interactive group is brought into contact, the coating amount is in terms of solid content from the viewpoint of sufficient interaction formation with the plating catalyst or its precursor. And 0.1 to 10 g / m ² is preferable, and 0.5 to 5 g / m ² is particularly preferable.
In addition, when a composition containing a compound having a polymerizable group and an interactive group is applied on a substrate and dried to form a layer containing a compound having a polymerizable group and an interactive group, Between the application and the drying, the remaining solvent may be removed by leaving at 30 to 80 ° C. for 30 minutes to 1 hour.

(Granting energy)
As a method for applying energy to the substrate surface, for example, radiation irradiation such as heating or exposure can be used. For example, light irradiation with a UV lamp, visible light, or the like, heating with a hot plate, or the like is possible. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
Specific examples generally used include direct image-like recording using a thermal recording head, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
The time required for applying energy is usually between 10 seconds and 5 hours, although it varies depending on the amount of the graft polymer produced and the light source.

In the case of performing the application of energy by the exposure, the exposure power, because to easily proceed the graft polymerization, addition, in order to suppress the decomposition of the produced graft ^polymer, of 100mJ / cm ² ~5000mJ / cm 2 A range is preferable.
In addition, when a polymer having an average molecular weight of 20,000 or more and a polymerization degree of 200 or more is used as the compound having a polymerizable group and an interactive group, the graft polymerization proceeds easily with low energy exposure. Degradation of the polymer can be further suppressed.

  By the step (a1) described above, a polymer layer (graft polymer layer) composed of a graft polymer having an interactive group can be formed on the substrate.

  When the obtained polymer layer is, for example, added to an alkaline solution having a pH of 12 and stirred for 1 hour and the decomposition of the polymerizable group site is 50% or less, the polymer layer is washed with a highly alkaline solution. It can be carried out.

[Step (a2)]
In the step (a2), a plating catalyst capable of multidentate coordination or a precursor thereof is imparted to the polymer layer formed in the step (a1). In this step, the interactive group possessed by the graft polymer constituting the polymer layer attaches (adsorbs) the applied plating catalyst or its precursor depending on its function.
Here, examples of the plating catalyst or a precursor thereof include those that function as a plating catalyst or an electrode in the plating step (a4) described later. Therefore, the plating catalyst or its precursor is determined by the type of plating in the (a4) plating step.
Here, the plating catalyst or its precursor used in this step is preferably an electroless plating catalyst or its precursor.

(Electroless plating catalyst)
As the plating catalyst used in the present invention, any catalyst can be used as long as it can be multidentately coordinated. Specifically, it can be multidentately coordinated and has a catalytic ability for an autocatalytic reduction reaction. Specific examples of the metal include Pd, Ag, Cu, Ni, Al, Fe, and Co. Among these, Pd is particularly preferable because of the type of functional group capable of multidentate coordination and high catalytic ability.

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

In practice, the metal ion that is the electroless plating precursor is applied onto the polymer layer using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in an appropriate 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. From the viewpoint of the type of functional group capable of multidentate coordination and high catalytic ability. , Pd ions are preferable in terms of catalytic ability.

As a method for applying a metal that is an electroless plating catalyst or a metal salt that is an electroless plating precursor to a polymer layer, a dispersion in which a metal is dispersed in an appropriate dispersion medium or a metal salt with an appropriate solvent. A solution containing dissolved and dissociated metal ions is prepared, and the dispersion or solution is applied on the polymer layer, or the substrate on which the polymer layer is formed is immersed in the dispersion or solution. By contacting an electroless plating catalyst or a precursor thereof, an interaction group in the polymer layer is utilized by an intermolecular force such as van der Waals force or a coordinate bond by a lone electron pair. Thus, the electroless plating catalyst or its precursor can be adsorbed.
From the viewpoint of sufficiently performing such adsorption, the metal concentration in the dispersion to be contacted or the metal ion concentration in the solution is preferably in the range of 0.01 to 50% by mass, More preferably, it is in the range of ˜30% by mass. The contact time is preferably about 1 minute to 24 hours, more preferably about 1 minute to 1 hour.

(Other catalysts)
In the present invention, a zero-valent metal can be used as a catalyst used for direct electroplating without performing electroless plating on the polymer layer in the step (a4) described later. Examples of the zero-valent metal include Pd, Ag, Cu, Ni, Al, Fe, Co, and the like. In particular, Pd, Ag, Cu are used because of their high adsorptive (adhesive) property to interactive groups and high catalytic ability. Is preferred.
This catalyst functions as an electrode for electroplating in the step (a4).
In addition, as a method for applying the other catalyst to the polymer layer, the same method as the method for applying the electroless plating or its precursor is used.

  Through the step (a2) described above, an interaction can be formed between the interactive group in the polymer layer and the plating catalyst or its precursor.

[Step (a3)]
In the step (a3), the polymer layer contains a metal different from the plating catalyst capable of multidentate coordination or a precursor thereof (hereinafter sometimes referred to as “foreign metal”).
This step may be performed on the polymer layer to which the multidentate plating catalyst or precursor thereof applied in the step (a2) is applied, or the polymer layer in the step (a1). It may be performed simultaneously with the formation. That is, in the latter case, in the step (a1), when a polymer layer is formed using a composition containing a compound having a polymerizable group and an interactive group, a foreign metal is previously contained in the composition. By disposing, a different metal can be contained in the formed polymer layer.
The dissimilar metal may be contained in the polymer layer as metal ions.

As the dissimilar metal used in this step, any metal can be used as long as it is a metal different from the plating catalyst or precursor thereof capable of multidentate coordination used in step (a2). It is preferable to form (adsorb) an interaction with a functional group and to function as an electroless plating catalyst or an electrode. Therefore, the dissimilar metal used in the step (a3) is preferably determined depending on the type of plating in the step (a4) described later.
Specifically, the dissimilar metal used in this step is silver (Ag), copper (Cu), nickel (Ni), cobalt (Co), tin (Sn), chromium (Cr), or zinc (Zn). Among them, silver, copper, or nickel is more preferable because of its good adaptability to electroless plating.

As a method of applying these different metals to the polymer layer to which the multidentate plating catalyst or precursor thereof applied in the step (a2) is applied, the different metals are dispersed in an appropriate dispersion medium. Prepare a dispersion or a solution containing dissociated metal ions dissolved in an appropriate solvent, and apply the dispersion or solution on the polymer layer, or form a polymer layer in the dispersion or solution. What is necessary is just to immerse the done substrate. The given dissimilar metal is used for the interaction group in the polymer layer by utilizing the interaction by intermolecular force such as van der Waals force or the coordinate bond by the lone electron pair (unshared electron pair). Adsorbed.
From the viewpoint of sufficiently performing such adsorption, the metal concentration in the dispersion to be contacted or the metal ion concentration in the solution is preferably in the range of 0.01 to 50% by mass, More preferably, it is in the range of ˜30% by mass. The contact time is preferably about 1 minute to 24 hours, more preferably about 1 minute to 1 hour.

  Moreover, when using the method of making a different metal contain in the composition containing the compound which has a polymeric group and an interactive group as this process, 0.01-100 with respect to the solid content of the composition. It is preferable to contain a dissimilar metal in the range of mass%, and more preferably in the range of 0.1 to 50 mass%.

  By going through the step (a3) as described above, the polymer layer contains a different metal in addition to the plating catalyst or its precursor.

[Step (a4)]
In the step (a4), a plating film is formed by performing plating on the polymer layer to which the electroless plating catalyst or its precursor has been applied. The formed plating film has excellent conductivity and adhesion.
Examples of the type of plating performed in this step include electroless plating and electroplating. In the steps (a2) and (a3), the plating catalyst or its precursor that forms an interaction with the polymer layer. It can be selected according to the function of the body and the different metal.
That is, in this step, electroplating or electroless plating may be performed on the polymer layer provided with the plating catalyst or its precursor.
Among them, in the present invention, it is preferable to perform electroless plating from the viewpoint of improving the formability and adhesiveness of the hybrid structure that appears in the polymer layer. In order to obtain a plating layer having a desired film thickness, it is a more preferable aspect that electroplating is further performed after electroless plating.
Hereinafter, the plating suitably performed in this process will be described.

(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 performed, for example, by rinsing a substrate to which an electroless plating catalyst and a different metal have been added to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. Do. As the electroless plating bath to be used, a generally known electroless plating bath can be used.
In addition, when the electroless plating catalyst precursor and the substrate provided with the different metal ions are immersed in the electroless plating bath in a state where the electroless plating catalyst precursor and the different metal ions are adsorbed or impregnated in the polymer layer. After the substrate is washed with water to remove excess precursors (such as metal salts), the substrate is immersed in an electroless plating bath. In this case, in the electroless plating bath, the electroless plating catalyst precursor and the different metal ions are reduced and subsequently electroless plating is performed. As the electroless plating bath used here, a generally known electroless plating bath can be used as described above.
In addition, the electroless plating catalyst precursor and the reduction of the different metal ions are separately prepared before the electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the above-described embodiment using the electroless plating liquid. It can also be performed as a process. The catalyst activating liquid is a liquid in which an electroless plating catalyst precursor (mainly metal ions) and a reducing agent capable of reducing dissimilar metal ions to zero-valent metals are dissolved, and is 0.1% to 50%, preferably 1%. ~ 30% is good. As the reducing agent, boron-based reducing agents such as sodium borohydride and dimethylamine borane, and reducing agents such as formaldehyde and hypophosphorous acid can be used.

The composition of a general electroless plating bath is as follows: 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath, and copper and gold are particularly preferable from the viewpoint of conductivity.
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, a chelating agent such as EDTA or Rochelle salt, which is a stabilizer of copper ions, and a trialkanolamine. . 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 thickness of the plating film formed by electroless plating can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. From the viewpoint, it is preferably 0.5 μm or more, and more preferably 3 μm or more.
Further, the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.

  The electroless-plated plating film obtained as described above has fine particles composed of electroless plating catalyst, dissimilar metal, and plating metal dispersed in the polymer layer by cross-sectional observation with SEM. It was confirmed that the plating metal was deposited on the layer. Since the interface between the substrate and the plating film is a hybrid state of polymer and fine particles, the interface between the substrate (organic component) and the inorganic substance (catalyst metal or plating metal) is smooth (for example, the unevenness difference is 500 nm or less). However, the adhesion is good.

(Electroplating)
In this step, when the dissimilar metal contained in the polymer layer in step (a3) and the metal catalyst contained in the polymer layer in step (a3) has a function as an electrode, the catalyst or its precursor Electroplating can be performed on the polymer layer provided with the body.
In addition, after the above-described electroless plating, the formed plating film may be used as an electrode, and electroplating may be further performed. As a result, a new metal film having an arbitrary thickness can be easily formed on the electroless plating film having excellent adhesion to the substrate. Thus, since electroplating is performed after electroless plating, the metal film can be formed to a thickness according to the purpose, and therefore, the metal film of the present invention is suitable for various applications.

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

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

In the present invention, the metal or metal salt derived from the above-described plating catalyst, plating catalyst precursor, and / or metal deposited in the polymer layer by electroless plating is used as a fractal microstructure in the layer. By being formed, the adhesion between the metal film and the polymer layer can be further improved.
The amount of metal present in the polymer layer is 5-50% by area of the metal in the region from the outermost surface of the polymer layer to a depth of 0.5 μm when the substrate cross section is photographed with a metal microscope. When the arithmetic average roughness Ra (JIS B0633-2001) between the polymer layer and the metal interface is 0.05 μm to 0.5 μm, a stronger adhesion is exhibited.

<Method for producing metal pattern material (1)>
The first aspect of the method for producing a metal pattern material of the present invention has (b1) a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof on a substrate, And (b2) providing a plating catalyst or precursor thereof capable of multidentate coordination to the polymer layer, and (b3) the polymer. A step of providing a layer with a metal different from the plating catalyst capable of multidentate coordination or a precursor thereof, and (b4) a step of plating the plating catalyst capable of multidentate coordination or a precursor thereof; And (b5) etching the formed plating film into a pattern.
Hereinafter, steps (b1) to (b5) in the metal pattern material manufacturing method (1) will be described.

[Step (b1)]
In the step (b1), the substrate has a non-dissociable functional group (interactive group) capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor, and is directly chemistry with the substrate. A polymer layer is formed of the bound polymer.
The step (b1) in the method (1) for producing the metal pattern material is the same as the step (a1) in the method for producing the substrate with a metal film, and the preferred embodiment is also the same.

[Step (b2)]
In the step (b2), a plating catalyst capable of multidentate coordination or a precursor thereof is imparted to the polymer layer formed in the step (b1).
The step (b2) in the method (1) for producing the metal pattern material is the same as the step (a2) in the method for producing the substrate with a metal film, and the preferred embodiment is also the same.

[Step (b3)]
In the step (b3), the polymer layer contains a metal (different metal) different from the plating catalyst capable of multidentate coordination or its precursor.
The step (b3) in the method (1) for producing the metal pattern material is the same as the step (a3) in the method for producing the substrate with a metal film, and the preferred embodiment is also the same.

[Step (b4)]
In the step (b4), plating is performed on the plating catalyst or precursor thereof capable of multidentate coordination imparted to the polymer layer in the step (b2).
The step (b4) in the method (1) for producing the metal pattern material is the same as the step (a4) in the method for producing the substrate with a metal film, and the preferred embodiment is also the same.

[Step (b5)]
In step (b5), the plating film formed in step (b4) is etched into a pattern. That is, in this step, a desired metal pattern can be formed by removing unnecessary portions of the plating film formed on the entire substrate surface by etching.
Any method can be used to form the metal pattern, and specifically, a generally known subtractive method or semi-additive method is used.

  With the subtractive method, a dry film resist layer is provided on the formed plating film, the same pattern as the metal pattern part is formed by pattern exposure and development, the plating film is removed with an etching solution using the dry film resist pattern as a mask, This is a method of forming a metal pattern. Any material can be used as the dry film resist, and negative, positive, liquid, and film-like ones can be used. Moreover, as an etching method, any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, wet etching is preferable because the apparatus is simple. As an etching solution, for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.

  Also, the semi-additive method is to provide a dry film resist layer on the formed plating film, form the same pattern as the non-metallic pattern part by pattern exposure and development, and perform electroplating using the dry film resist pattern as a mask. In this method, quick etching is performed after removing the dry film resist pattern, and the plating film is removed in a pattern to form a metal pattern. The dry film resist, etching solution, etc. can use the same material as the subtractive method. Further, as the electroplating technique, the technique described above can be used.

  Through the above steps, a metal pattern material having a desired metal pattern is produced.

<Method for producing metal pattern material (2)>
The second aspect of the method for producing a metal pattern material of the present invention has (c1) a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof on a substrate, And a step of forming a polymer layer comprising a polymer directly chemically bonded to the substrate in a pattern, (c2) a step of applying a plating catalyst capable of multidentate coordination or a precursor thereof to the polymer layer, and (c3) ) A step in which the polymer layer contains a metal different from the plating catalyst or precursor thereof capable of multidentate coordination; and (c4) plating is applied to the plating catalyst or precursor thereof capable of multidentate coordination. And a process.
That is, in the method (1) for producing the metal pattern material, a desired metal pattern is formed by forming a polymer layer over the entire surface of the substrate and removing the plating film formed on the polymer layer. In the method (2) for producing the metal pattern material, a polymer layer is formed in a pattern on a substrate, and a metal pattern corresponding to the patterned polymer layer is formed.

  Hereinafter, steps (c1) to (c4) in the metal pattern material manufacturing method (2) will be described.

[Step (c1)]
In the step (c1), a polymer comprising a non-dissociative functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof on the substrate, and which is directly bonded to the substrate. The layer is formed in a pattern. The step (c1) in the method (2) for producing the metal pattern material is in accordance with the means described in the step (a1) in the method for producing the substrate with the metal film. In the substrate manufacturing method, the polymer layer is formed on the entire surface of the substrate, but in this embodiment, the polymer layer is formed in a pattern.
More specifically, when the surface graft polymerization method is used in the step (a1) in the method for manufacturing the substrate with a metal film, a polymer layer is formed by applying energy to the entire surface of the substrate. In the step), in the formation of the polymer layer, energy is imparted in a pattern to form the polymer layer in a pattern.

  (C1) Substrate with metal film for details such as substrate (intermediate layer that can be formed on the substrate, polymerization initiation layer), matters relating to each element constituting the polymer layer, etc. applied to the step The matters described in the step (a1) of the production method (1) can be similarly applied.

(Granting energy)
In the step (c1), the method for applying energy in a pattern is not particularly limited, and any method can be used as long as it can apply energy capable of generating active sites on the substrate surface in a pattern.
As means for applying energy to the pattern, for example, light irradiation with an infrared laser, ultraviolet lamp, visible light, electron beam irradiation such as γ rays, thermal recording with a thermal head, etc. are possible, From the viewpoint of simplicity of the apparatus, a method of irradiating actinic rays is preferable. Examples of these light sources include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps. 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.
Specific examples generally used include direct image-like recording using a thermal recording head, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
When applying actinic ray irradiation in a pattern, both scanning exposure based on digital data and pattern exposure using a lith film can be used.

  By applying pattern-like energy in this way, the active sites generated on the substrate surface and the compound having a polymerizable group and an interactive group are polymerized, so that the graft polymer is formed only in the region to which energy is applied. Generate.

[(C2) step, (c3) step, and (c4) step]
The (c2) step, (c3) step, and (c4) step in the metal pattern material manufacturing method (2) are respectively the (a2) step, (a3) step, and ( It is the same as the step a4) and the preferred embodiment is also the same.

  By passing through the above process, the metal pattern material which has a metal pattern corresponding to the pattern of a polymer layer is produced.

<Substrate with metal film and metal pattern material>
The substrate with a metal film and the metal pattern material of the present invention are obtained by the method for producing the substrate with a metal film of the present invention and the method for producing the metal pattern material.
The obtained metal film-coated substrate and the polymer layer constituting the metal pattern material, as described above, interact with the plating catalyst or its precursor, but are non-dissociable and more hydrophilic than the dissociable group. Since the polymer layer itself has a low functional group, the polymer layer itself has low hydrophilicity and low temperature / humidity dependency. As a result, it is possible to prevent the metal film (plating) or substrate formed on the polymer layer from being deformed.
Further, even if the polymer layer is a metal pattern material (metal pattern material obtained by the metal pattern material manufacturing method (1) of the present invention) in which the metal pattern remains in the non-formation region of the metal pattern, Therefore, the insulation reliability is excellent.
On the other hand, the metal pattern material obtained by the method (2) for producing the metal pattern material of the present invention has a form in which no polymer layer is present in the non-formation region of the metal pattern, and therefore has excellent insulation reliability.

  The substrate with a metal film and the metal pattern material of the present invention may have a metal film (plating film) provided on the entire surface or locally on the substrate having a surface irregularity of 500 nm or less (more preferably 100 nm or less). preferable. Moreover, it is preferable that the adhesiveness of a board | substrate and a metal film (metal pattern) is 0.2 kN / m or more. That is, the substrate surface is smooth, and the adhesion between the substrate and the metal film (metal pattern) is excellent.

The unevenness of the substrate surface is a value measured by cutting the substrate perpendicular to the substrate surface and observing the cross section with an SEM.
More specifically, Rz measured in accordance with JIS B 0601, that is, “the difference between the average value of the Z data of the peak from the maximum to the fifth in the designated plane and the average value of the valley from the minimum to the fifth. ”Is preferably 500 nm or less.
The adhesion value between the substrate and the metal film was determined by bonding a copper plate (thickness: 0.1 mm) to the surface of the metal film with an epoxy adhesive (Araldite, manufactured by Ciba Geigy) and drying at 140 ° C. for 4 hours. After that, the 90 degree peeling experiment is performed based on JIS C 6481, or the end portion of the metal film itself is directly peeled off, and the 90 degree peeling experiment is performed based on JIS C 6481.

The substrate with a metal film obtained by the method for producing a substrate with a metal film of the present invention can be used, for example, as an anti-electromagnetic wave film or by patterning a metal film (plating film) by etching. The present invention can be applied to various uses such as a wiring board, FPC, COF, TAB, antenna, multilayer wiring board, and mother board.
Moreover, the metal pattern material obtained by the metal pattern material production methods (1) and (2) can also be applied to the above-described various uses.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Unless otherwise specified, “%” and “part” are based on mass.

[Example 1]
[Production of substrate]
An epoxy insulating film GX-13 (film thickness: 45 μm) manufactured by Ajinomoto Fine Techno Co., Ltd. is heated and pressurized on a glass epoxy substrate as an electrical insulating layer, and 100 ° C. to 110 ° C. at a pressure of 0.2 MPa using a vacuum laminator. The base material A was obtained by bonding under the above conditions.
Next, an insulating composition containing a polymerization initiator having the following composition is applied onto the base material A by spin coating so as to have a thickness of 3 microns, and left at 30 ° C. for 1 hour to remove the solvent. Then, it was dried at 170 ° C. for 30 minutes to form a polymerization initiation layer (insulating polymerization initiation layer).

(Insulating composition containing a polymerization initiator)
20 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.), cresol novolac type epoxy resin (epoxy equivalent 215, Epiklon N-673 manufactured by Dainippon Ink & Chemicals, Inc.) 45 30 parts by mass of phenol novolac resin (phenolic hydroxyl group equivalent 105, phenolite manufactured by Dainippon Ink & Chemicals, Inc.) in 20 parts by mass of ethyl diglycol acetate and 20 parts of solvent naphtha are heated and dissolved with stirring. After cooling to room temperature, 30 parts by mass of cyclohexanone varnish (YL6747H30 manufactured by Yuka Shell Epoxy Co., Ltd., nonvolatile content 30 mass%, weight average molecular weight 47000) of phenoxy resin composed of Epicoat 828 and bisphenol S, 2- Phenyl-4,5 0.8 parts by mass of bis (hydroxymethyl) imidazole, 2 parts by mass of finely pulverized silica, and 0.5 parts by mass of a silicon-based antifoaming agent were added, and polymerization initiator polymer P synthesized by the following method was added to this mixture. 10 parts was added to obtain an insulating composition containing a polymerization initiator.

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

  After the polymerization initiation layer as described above was formed, a curing treatment was performed at 180 ° C. for 30 minutes. Thereby, a substrate A1 was obtained. The surface roughness (Rz) of this substrate A1 was 0.1 μm.

[Formation of polymer layer]
(Synthesis of Polymer 1 having Polymerizable Group and Interactive Group)
First, polymer 1 having a polymerizable group and an interactive group was synthesized as follows.
In a 1000 ml three-necked flask, 20 g of N, N-dimethylacetamide was placed and heated to 75 ° C. under a nitrogen stream. A solution of 8.6 g of 2-hydroxyethyl acrylate, 31.1 g of 4-vinylpyridine (a monomer having an interactive group), and 0.85 g of V-601 (manufactured by Wako Pure Chemical Industries), 20 g of N, N-dimethylacetamide, The solution 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 above reaction solution, 0.37 g of ditertiary pentyl hydroquinone, 0.47 g of dibutyltin dilaurate, 23.3 g of Karenz AOI (manufactured by Showa Denko KK), 25 g of N, N-dimethylacetamide were added at 55 ° C. for 4 hours. Reaction was performed. Thereafter, 20.0 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 performed, the solid matter was collected by filtration, washed with water, and dried to obtain 15 g of polymer 1 (the following structure) having a polymerizable group and an interactive group.
“Karenz AOI” is one of the monomers having a polymerizable group and has an isocyanate group.

(Generation of graft polymer)
Polymer having a polymerizable group and an interactive group 1: 9.6 parts by mass, 76.0 parts by mass of isopropanol, 33.9 parts by mass of methanol, and 4.8 parts by mass of N, N dimethylacetamide were mixed and stirred. A solution was prepared.
Subsequently, the prepared coating solution was applied by spin coating so as to have a thickness of 1.0 μm on the polymerization initiation layer of the substrate A by spin coating, and dried at 80 ° C. for 30 minutes. Using a UV exposure machine (model number: UVF-502S, lamp: UXM-501MD) manufactured by Mitsunaga Electric, an irradiation power of 1.5 mW / cm ² (Ushio UV integrated light meter UIT150-light receiving sensor UVD-S254) In irradiation power measurement), irradiation was performed for 660 seconds to generate a graft polymer on the entire surface of the polymerization initiation layer of the substrate A1.

Thereafter, the substrate A1 on which the graft polymer was produced was immersed in stirred methanol for 5 minutes, and then washed with distilled water.
Thereby, a substrate A2 having a polymer layer was obtained.

[Applying plating catalyst]
The substrate A2 having the polymer layer was immersed in a 0.2% by mass palladium chloride aqueous solution for 10 minutes, and then immersed in distilled water for cleaning.
Subsequently, the substrate A2 having a polymer layer is immersed in 1 L of water in a catalyst activation liquid (reducing liquid) prepared by adding the treatment liquid MRD2A: 18 mL and MRD2C: 60 mL manufactured by Uemura Kogyo for 5 minutes. Then, it was immersed in distilled water and washed.

[Applying dissimilar metals]
Next, the substrate A2 having a polymer layer was immersed in a 1% by mass silver nitrate aqueous solution for 10 minutes, and then immersed in distilled water for cleaning.

[Electroless plating]
As described above, electroless plating was performed on the substrate A2 having the polymer layer provided with the plating catalyst at 60 ° C. for 5 minutes using an electroless plating bath having the following composition. The thickness of the obtained electroless copper plating film was 0.3 μm.

(Composition of electroless plating bath)
・ Distilled water 1709g
・ Copper sulfate 18.1g
・ Ethylenediaminetetraacetic acid disodium salt 54.0g
・ Polyoxyethylene glycol (molecular weight 1000) 0.18g
・ 2,2'bipyridyl 1.8mg
・ 10% ethylenediamine aqueous solution 7.1g
・ 37% formaldehyde aqueous solution 9.8g
The pH of the above plating bath composition was adjusted to 12.5 (60 ° C.) with sodium hydroxide and sulfuric acid.

[Electroplating]
Subsequently, electroplating was performed for 30 minutes under the conditions of 3 A / dm ² using an electroless copper plating film as a power feeding layer and using an electrolytic copper plating bath having the following composition. The thickness of the obtained electrolytic copper plating film was 18 μm. This obtained board | substrate A3 with a metal film.

(Composition of electroplating bath)
・ Copper sulfate 38g
・ 95 g of sulfuric acid
・ Hydrochloric acid 1mL
・ Copper Greeme PCM (Meltex Co., Ltd.) 3mL
・ Water 500g

(Adhesion evaluation)
Using a tensile tester (RTM-100, manufactured by A & D Co., Ltd.), the plated film of the obtained substrate A3 with metal film was 90 mm at a tensile strength of 10 mm / min with a width of 5 mm. The peel strength was measured and found to be 0.65 kN / mm.

(Insulation reliability test)
An etching resist is formed in the region to be left as a metal pattern (wiring pattern) on the surface of the plating film of the obtained substrate A3 with metal film, and the plating film in the region without the resist is removed with an etching solution made of FeCl ₃ / HCl. did. Thereafter, the etching resist was removed with an alkaline stripping solution made of 3% NaOH solution to form a comb-like wiring for measuring line-to-space = 100 μm / 100 μm line-to-line insulation reliability.
This comb-shaped wiring was allowed to stand at 125 ° C.-85% relative humidity (unsaturated), applied voltage 10 V, 2 atm for 200 hours with an ESPEC HAST tester (AMI-150S-25), between the wiring There was no insulation failure.
Thus, since no insulation failure is observed even when left under high temperature and high humidity, it can be seen that the polymer layer constituting this comb-shaped wiring has low water absorption and low temperature / humidity dependency. That is, it can be seen that the polymer layer constituting the metal film-coated substrate A3 before forming the comb-like wiring also has low water absorption and low temperature / humidity dependency.

[Example 2]
A substrate with a metal film was obtained in the same manner as in Example 1 except that the aqueous solution of different metals used in Example 1 was changed to a 1 wt% nickel sulfate hexahydrate aqueous solution. It was 0.64 kN / m when the 90 degree peel strength of the obtained board | substrate with a metal film was measured by the method similar to Example 1. FIG.
Further, as a result of conducting an insulation reliability test in the same manner as in Example 1, no insulation failure was found between the wirings.

Example 3
In Example 1, 33.9 parts by mass of methanol constituting the coating solution containing the polymer 1 having a polymerizable group and an interactive group was changed to 33.9 parts by mass of an ethanol solution of 1% silver trifluoroacetate. Except for this, a substrate with a metal film was obtained in the same manner as in Example 1. It was 0.68 kN / m when the 90 degree peel strength of the obtained board | substrate with a metal film was measured by the method similar to Example 1. FIG.
Further, as a result of conducting an insulation reliability test in the same manner as in Example 1, no insulation failure was found between the wirings.

  From the above results, it can be seen that according to the present invention, the metal film (metal pattern) can be formed with good adhesion to a smooth substrate and the insulation reliability of the non-formation region of the metal pattern is excellent. Therefore, the printed wiring board excellent in electrical reliability can be obtained by using the board | substrate (metal pattern material) with a metal film obtained by this invention.

Claims (13)

(A1) On the substrate, a polymer layer made of a polymer having a non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor and directly chemically bonded to the substrate is formed. And a process of
(A2) providing a plating catalyst capable of multidentate coordination or a precursor thereof to the polymer layer;
(A3) a step of causing the polymer layer to contain a metal different from the plating catalyst or precursor thereof capable of multidentate coordination;
(A4) a step of plating the plating catalyst or precursor thereof capable of multidentate coordination;
A method for manufacturing a substrate with a metal film, comprising:   The non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or a precursor thereof is a nitrogen-containing functional group, an oxygen-containing functional group, or a sulfur-containing functional group. 2. A method for producing a substrate with a metal film according to 1.   The metal film according to claim 1 or 2, wherein the non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or a precursor thereof is a nitrogen-containing functional group. A method for manufacturing a substrate.   The method for producing a substrate with a metal film according to any one of claims 1 to 3, wherein the plating catalyst capable of multidentate coordination or a precursor thereof is palladium or palladium ions.   The metal different from the plating catalyst or precursor thereof capable of multidentate coordination is silver, copper, nickel, cobalt, tin, chromium, or zinc. 2. A method for manufacturing a substrate with a metal film according to item 1.   The board | substrate with a metal film obtained by the manufacturing method of the board | substrate with a metal film of any one of Claims 1-5. (B1) On the substrate, a polymer layer made of a polymer having a non-dissociative functional group capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor and directly chemically bonded to the substrate is formed. And a process of
(B2) providing a plating catalyst capable of multidentate coordination or a precursor thereof to the polymer layer;
(B3) adding a metal different from the plating catalyst capable of multidentate coordination or a precursor thereof to the polymer layer;
(B4) a step of plating the plating catalyst capable of multidentate coordination or a precursor thereof;
(B5) etching the formed plating film into a pattern;
A method for producing a metal pattern material characterized by comprising: (C1) A polymer layer having a non-dissociable functional group capable of multidentate coordination that forms an interaction with a plating catalyst or a precursor thereof on the substrate and made of a polymer directly chemically bonded to the substrate is patterned. Forming into a shape,
(C2) providing a plating catalyst capable of multidentate coordination or a precursor thereof to the polymer layer;
(C3) adding a metal different from the plating catalyst or precursor thereof capable of multidentate coordination to the polymer layer;
(C4) a step of plating the plating catalyst or precursor thereof capable of multidentate coordination;
A method for producing a metal pattern material characterized by comprising:   The non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or a precursor thereof is a nitrogen-containing functional group, an oxygen-containing functional group, or a sulfur-containing functional group. The manufacturing method of the metal pattern material of Claim 7 or Claim 8.   The non-dissociable functional group capable of multidentate coordination that forms an interaction with the plating catalyst or its precursor is a nitrogen-containing functional group, according to any one of claims 7 to 9. The manufacturing method of the metal pattern material of description.   The method for producing a metal pattern material according to claim 7, wherein the plating catalyst capable of multidentate coordination or a precursor thereof is palladium or palladium ions.   The metal different from the plating catalyst or precursor thereof capable of multidentate coordination is silver, copper, nickel, cobalt, tin, chromium, or zinc. 2. A method for producing a metal pattern material according to item 1.   The metal pattern material obtained by the manufacturing method of the metal pattern material of any one of Claims 7-12.