JP4712420B2 - Surface graft material, conductive material and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing a surface graft material useful for forming a conductive material, and a surface graft material and a conductive material obtained thereby, and more particularly, a conductive film used in the field of electronic materials, in particular, The present invention relates to a method for producing a surface graft material useful for forming a copper-clad laminate used for metal wiring boards and printed wiring boards.

A “subtractive method” is known as a metal pattern forming method useful in the field of conventional conductive patterns, particularly printed wiring boards. In the subtractive method, a metal layer formed on a substrate is provided with a photosensitive layer that is exposed by irradiation with actinic rays, and this photosensitive layer is imagewise exposed and developed to form a resist image. Is a method of forming a metal pattern by etching, and finally stripping the resist. In the metal substrate used in this method, in order to provide adhesion between the substrate and the metal layer, the substrate interface has been subjected to uneven treatment to develop adhesion by the anchor effect. As a result, the substrate interface portion of the resulting metal pattern becomes uneven, and there is a problem in that the high frequency characteristics deteriorate when used as electrical wiring. Further, when forming the metal substrate, there is a problem that a complicated process of treating the substrate with a strong acid such as chromic acid is necessary in order to process the unevenness of the substrate.
In order to solve this problem, a method has been proposed in which a radically polymerizable compound is grafted on the surface of the substrate to modify the surface, thereby minimizing the unevenness of the substrate and simplifying the substrate processing process. However, this method requires an expensive device (γ ray generator, electron beam generator). In addition, since the substrate used is a normal commercially available plastic substrate, the graft polymer is not sufficiently produced so that the conductive material is firmly attached thereto, and the substrate and the conductive layer are not sufficiently formed. There was a problem that adhesion did not reach practical strength.
JP 58-196238 A

The purpose of the present invention, which was made in consideration of the above-mentioned conventional technical problems, is a surface graft polymer material that is excellent in adhesion to a substrate and is useful for forming a conductive film with small irregularities at the interface with the substrate, and It is in providing the manufacturing method. Another object of the present invention is to provide a metal substrate having these two characteristics, that is, a conductive material and a manufacturing method thereof.
The conductive material obtained according to the present invention is useful as a copper-clad multilayer substrate useful for forming fine patterns with excellent high-frequency characteristics, and a circuit is formed by a subtractive method using this copper-clad multilayer substrate. Then, a fine printed wiring board can be created.

As a result of intensive studies, the present inventor has found that the above problem can be solved by providing a graft polymer layer on the surface of a specific insulator layer, and has completed the present invention.
That is, the configuration of the present invention is as follows.
<1> A step of providing an insulator layer containing a polymerization initiator in an insulating resin on a support, and a step of forming a graft polymer directly bonded to the surface of the insulator layer, in order. A method for producing a surface graft material.
<2> A surface graft material produced by the method for producing a surface graft according to <1>.
<3> A step of providing an insulator layer containing a polymerization initiator in an insulating resin on a support, a step of forming a graft polymer directly bonded to the surface of the insulator layer, a conductive property on the graft polymer A method for producing a conductive material, comprising sequentially providing a layer.
<4> A conductive material produced by the method for producing a conductive material according to <3>.
<5> A conductive pattern material obtained by etching a conductive material produced by the method for producing a conductive material according to <3>.

According to the present invention, it is possible to provide a surface graft polymer material that is excellent in adhesion to a substrate and that is useful for forming a conductive film with small irregularities at the interface with the substrate, and a method for producing the same.
Another object of the present invention is to provide a metal substrate that is excellent in adhesion to the substrate and has small irregularities at the interface with the substrate, that is, a conductive material and a method for producing the same.
The conductive material obtained according to the present invention is useful as a copper-clad multilayer substrate useful for forming fine patterns with excellent high-frequency characteristics, and a circuit is formed by a subtractive method using this copper-clad multilayer substrate. Then, a fine printed wiring board can be produced.

In the method for producing a surface graft material of the present invention, first, an insulator layer containing a polymerization initiator in an insulating resin is provided on an arbitrary support, and then polymerization contained in the insulator layer is performed. Surface graft polymerization is performed using the initiator as a base point to form a graft polymer directly bonded to the surface of the insulating resin layer.
In the present invention, the main feature is that an initiator-containing insulator layer is provided by including a polymerization initiator in an insulating resin such as an epoxy resin, a polyimide resin, a liquid crystalline resin, or a polyarylene resin. An insulating layer made of an insulating resin material having desired characteristics and having a polymerization initiating ability can be formed on an arbitrary support surface. Thereafter, by forming a graft polymer directly bonded to the surface of the formed insulating layer, a surface graft material that is smooth and can be attached with any material can be manufactured. By attaching a conductive material to the graft polymer in the surface graft material, a smooth and uniform conductive film can be formed.

In the present invention, by including a polymerization initiator in the insulating resin, the adhesion between the insulator layer and the graft is further strengthened, and a strong adhesion is exhibited.
The reason is not clear, but it can be considered that the addition of a polymerization initiator to the insulating resin layer increases the density of the surface graft, which increases the interaction with the conductive material layer and as a result, improves the adhesion. It is considered a thing.
Further, the present inventors have found that this technique is a wide technique that can be applied to general insulating resins useful in the field of electronic materials such as polyimide and epoxy resin.

  The effect of the present invention, that is, high adhesion between the insulating substrate and the conductive material is as follows. 1. a strong and dense bond between the substrate and the graft polymer; The produced graft polymer and the conductive material are exerted by the strong interaction. In order to exhibit these effects, it is important to select a compound that strongly interacts with the graft polymer and the conductive material in addition to adding a polymerization initiator in the insulating layer. Next, details of the invention will be described in order.

Hereinafter, the manufacturing method of the surface graft material of this invention is demonstrated in detail in order of a process.
[Step of providing an insulator layer containing a polymerization initiator in an insulating resin on a support]
As the insulating resin constituting the insulator layer in the present invention, a known insulating resin that has been used as a conventional multilayer laminate, a build-up substrate, or a flexible substrate can be used. As these resins, thermosetting resins, thermoplastic resins, or a resin mixture thereof can be used. In the present invention, the insulator layer is formed using these insulator resins containing a photopolymerizable initiator. A polyfunctional acrylate monomer may be added for the purpose of increasing the graft reactivity or the strength of the insulator layer. In addition, inorganic or organic particles may be added as other components in order to increase the strength of the insulator layer or improve the electrical characteristics.

Hereinafter, each component constituting the insulator layer according to the present invention will be described.
Specific examples of the thermosetting resin include, for example, an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, a polyolefin-based resin, and a isocyanate-based resin.
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, Examples thereof include cyclopentadiene type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, and alicyclic epoxy resins. These may be used alone or in combination of two or more. Thereby, it will be excellent in heat resistance.

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

Further, the epoxy resin will be described in detail.
The epoxy resin constituting the epoxy resin substrate in the present invention has (A) an epoxy compound having two or more epoxy groups in one molecule and (B) two or more functional groups reacting with the epoxy group in one molecule. It consists of a reaction product with a compound. The functional group in (B) is selected from functional groups such as a carboxyl group, a hydroxyl group, an amino group, and a thiol group.
(A) As an epoxy compound (including what is called an epoxy resin) having two or more epoxy groups in one molecule, an epoxy compound having 2 to 50 epoxy groups in one molecule is preferable. More preferably, the epoxy compound has 2 to 20 epoxy groups in one molecule. Here, the epoxy group should just be a structure which has an oxirane ring structure, For example, a glycidyl group, an oxyethylene group, an epoxy cyclohexyl group etc. can be shown. Such polyvalent epoxy compounds are widely disclosed in, for example, published by Masaki Shinbo “Epoxy Resin Handbook” published by Nikkan Kogyo Shimbun (1987), and these can be used.

  Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

  (B) As a compound having two or more functional groups that react with an epoxy group in one molecule, a polyfunctional carboxylic acid compound such as terephthalic acid, a polyfunctional hydroxyl compound such as a phenol resin, an amino resin, 1, 3, 5 -Polyfunctional amino compounds such as triaminotriazine can be mentioned.

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

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

(Compound having a polymerizable double bond)
In the insulating layer, a necessary compound can be added according to the purpose of use. As such a compound, there is a compound having a radical polymerizable double bond. The compound having a radical polymerizable double bond is an acrylate or methacrylate compound. The acrylate compound [(meth) acrylate] that can be used in the present invention is not particularly limited as long as it has an acryloyl group that is an ethylenically unsaturated group in the molecule, but is curable and the hardness of the formed intermediate layer. From the viewpoint of improving the strength, a polyfunctional monomer is preferable.
The polyfunctional monomer that can be suitably used in the present invention is preferably an ester of a polyhydric alcohol and acrylic acid or methacrylic acid. Examples of polyhydric alcohols include ethylene glycol, 1,4-cyclohexanol, pentaerythritol, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, polyurethane polyol and polyester polyol. . Of these, trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyol are preferable. The intermediate layer may contain two or more types of polyfunctional monomers. The polyfunctional monomer is one containing at least two ethylenically unsaturated groups in the molecule, and more preferably containing three or more. Specific examples include polyfunctional acrylate monomers having 3 to 6 acrylate groups in the molecule, and several acrylic acids in the molecule called urethane acrylate, polyester acrylate, and epoxy acrylate. An oligomer having an ester group and having a molecular weight of several hundred to several thousand can be preferably used as a component of the intermediate layer of the present invention.

  Specific examples of acrylates having three or more acrylic groups in the molecule include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Examples thereof include polyol polyacrylates such as hexaacrylate, and urethane acrylates obtained by reaction of polyisocyanates with hydroxyl group-containing acrylates such as hydroxyethyl acrylate. In addition, as a compound having a polymerizable double bond, a thermosetting resin, or a thermoplastic resin, for example, an epoxy resin, a phenol resin, a polyimide resin, a polyolefin resin, a fluorine resin, etc., using methacrylic acid or acrylic acid, A resin obtained by subjecting a part of the resin to a (meth) acrylation reaction may be used. Specific examples include (meth) acrylate compounds of epoxy resins.

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

(Other additives)
The insulator layer in the present invention is a composite of a resin and other components (composite material) in order to reinforce the mechanical strength, heat resistance, weather resistance, flame resistance, water resistance, electrical characteristics, etc. of the resin. 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. When these materials are added, it is preferable to add them in the range of 1 to 200% by mass, and more preferably in the range of 10 to 80% by mass with respect to the resin. When this addition amount is less than 1% by mass, there is no effect of strengthening the above-mentioned properties, and when it exceeds 200% by mass, properties such as strength peculiar to the resin are reduced. The graft polymerization reaction also does not proceed.

(Shape: thickness, uneven surface etc.)
The insulator layer in the present invention can be formed on any support. Here, there is no restriction | limiting in particular as a support body, As long as it has a hard surface which can form an insulator layer, any may be sufficient.
The thickness of the formed insulator layer is generally in the range of 1 μm to 10 mm, and preferably in the range of 10 μm to 1000 μm. In addition, it is also preferable to use an insulating layer having an average roughness (Rz) measured by JIS B 0601 (1994), 10-point average height method of 3 μm or less, and Rz of 1 μm or less. More preferably.
If the surface smoothness of the formed insulator layer is within the above-mentioned range, that is, substantially without unevenness, the circuit is very fine (for example, a circuit having a line / space value of 25/25 μm or less. Pattern) It is suitably used when producing a printed wiring board.

[Step of forming graft polymer directly bonded to insulator layer surface]
In order to form a graft polymer directly bonded to the surface of the insulator layer thus provided, the surface of the insulator layer is contacted with a compound having an unsaturated double bond capable of radical polymerization, A method of exposing the film may be taken. The compound having an unsaturated double bond capable of radical polymerization used here preferably has a functional group capable of interacting with the substance to be attached to the graft pattern. For example, the conductive pattern described in detail below. In order to form the material, it is preferable to use a polymerizable compound having a functional group capable of interacting with the conductive material as the compound having an unsaturated double bond capable of radical polymerization.
A polymerizable compound having an unsaturated double bond capable of radical polymerization and having a functional group capable of interacting with a conductive material, as a means for contacting, a compound having an unsaturated double bond capable of radical polymerization, For example, a layer containing an unsaturated double bond capable of radical polymerization and a polymerizable compound having a functional group capable of interacting with a conductive material (hereinafter referred to as a graft polymer precursor layer as appropriate) is insulated. What is necessary is just to form in the body layer surface, and formation of this graft polymer precursor layer can be performed by the apply | coating method.
In addition to the polymerizable compound, the graft polymer precursor layer may contain other components for forming the layer, that is, a binder, a viscosity adjusting agent, a surfactant, and other film forming agents.

In the present invention, “unsaturated double bond capable of radical polymerization” necessary for bonding to the insulator layer and “conductive material necessary for adhering the conductive material described later to the graft polymer” are possible. It is preferable to use a polymerizable compound having both of the “functional group”.
As used herein, the radical polymerizable unsaturated double bond includes a vinyl group, a vinyloxy group, an allyl group, an acryloyl group, a methacryloyl group, and the like. Among these, the acryloyl group and the methacryloyl group are highly reactive, and good results are obtained.

  The functional group capable of interacting with the conductive material is a functional group having a positive charge such as ammonium or phosphonium, or a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group or a phosphonic acid group. Examples thereof include acidic groups that can be dissociated into negative charges. In addition, nonionic polar groups such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, and a cyano group can also be used.

  A polymerizable compound having an unsaturated double bond capable of radical polymerization and a functional group capable of interacting with a conductive material, which is an essential requirement of the present invention, is a polymer even if it is a low molecule. May be. In the case of a polymer, the average molecular weight is selected in the range of 1,000 to 500,000. Such a polymer can be obtained by methods such as addition polymerization such as normal radical polymerization and anion polymerization, and polycondensation.

  Specifically, in the present invention, the compound having an unsaturated double bond capable of radical polymerization and having a functional group capable of interacting with a conductive material is easy to attach and adsorb metal ions or metal salts. From the viewpoint of easy removal of unreacted substances after the graft reaction, a hydrophilic polymer, hydrophilic macromer, hydrophilic monomer or the like having a hydrophilic group that is a polar group is preferable.

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

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

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

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

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

It is essential that the hydrophilic polymer containing a radical polymerizable group has an unsaturated double bond capable of radical polymerization as a constituent component and has a functional group capable of interacting with a conductive material. In order to improve the film physical properties of the precursor layer and to improve the adhesion to the insulating resin substrate, it may be in the form of a terpolymer or quaternary copolymer including a copolymer component with other monomers. .
Copolymerization components with other monomers include alkyl acrylates such as methyl (meth) acrylate and butyl (meth) acrylate, ethylene glycol-based (meth) such as 2-methoxyethyl (meth) acrylate, polyethylene glycol acrylate and polypropylene acrylate. And acrylate.

[Other components that may be contained in the graft polymer precursor layer]
(binder)
If desired, the graft polymer precursor layer may contain a binder. The binder is used to form a precursor layer together with a radical polymerizable group-containing hydrophilic compound. In the case where the polymerizable group-containing hydrophilic compound can form a layer alone, it is not particularly necessary. It is preferable to do. The binder for this purpose is not particularly limited as long as it is mixed with a polymerizable group-containing hydrophilic compound and forms a film, but is preferably a water-soluble oligomer or polymer having a molecular weight of 500 or more.
These added polymers include polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polybutyral, polyvinylpyrrolidone, polyethylene oxide, polyethyleneimine, polyacrylamide, carboxymethylcellulose, hydroxyethylcellulose, (meth) acrylate polymers, sesulose polymers In addition to synthetic polymers such as, natural hydrophilic polymers such as gelatin, starch, gum arabic and sugar can be used.

(Plasticizer, surfactant, viscosity modifier)
It is used in order to give flexibility to the precursor layer and to prevent cracks in the precursor layer during bending in a film state. As the plasticizer, known materials that are generally used are used.

(solvent)
The above-mentioned components can be dissolved in an appropriate solvent, applied and dried to form a graft polymer precursor layer suitably required for the present invention.
As the solvent, water and an organic solvent are used. As the organic solvent, either a hydrophilic solvent or a hydrophobic solvent can be used, but a solvent having a high affinity for water is particularly useful. Specifically, alcohol solvents such as methanol, ethanol and 1-methoxy-2-propanol, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran, and nitrile solvents such as acetonitrile are preferable.

The thickness of the graft polymer precursor layer is preferably in the range of 0.5 μm to 10 μm. In this range, the thickness of the graft polymer layer to be formed thereafter becomes a suitable range, and in the subsequent process, for example, even when a conductive material is adhered, excellent adhesion to the conductive material can be secured. .
After formation of the graft polymer precursor layer, the thickness of the graft polymer layer generated in the overall exposure step is preferably in the range of 0.1 μm to 0.7 μm. Therefore, the thickness of the graft polymer precursor layer is more than 10 μm. Even if the thickness is increased, the number of materials not involved in the formation of the graft polymer increases, which not only leads to an increase in cost, but also makes it difficult for the exposure light source to reach the deep part, making it difficult to remove unnecessary graft polymer precursor materials. It brings many problems.

(Formation of graft polymer on insulating layer surface)
By exposing the graft precursor layer formed on the insulating layer as described above, radicals are generated from the precursor layer, and react with the upper graft precursor layer to thereby generate an insulating layer / precursor layer interface. A strong chemical bond is formed and a graft polymer is formed.
(Granting energy)
Formation of the graft polymer in the present invention is performed by irradiation with radiation such as heat or light. Heating is performed using a heater or infrared rays. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.

Various materials can be attached to the graft polymer obtained in this way depending on the functional group to be introduced, but it is particularly useful for providing a conductive material to form a conductive film. The obtained conductive film is excellent in adhesion to a smooth insulator layer.
[Step of applying a conductive material on the graft polymer directly bonded to the surface of the insulator layer]
As the step of imparting conductivity to the graft polymer, (1) a step of attaching conductive fine particles to the generated graft polymer, (2) a metal ion or a metal salt is imparted to the generated graft polymer, and then the metal ion Or a step of depositing metal by reducing metal ions in the metal salt, (3) a step of electroless plating by applying an electroless plating catalyst or a precursor thereof to the formed graft polymer, and (4) It is preferably any one selected from the steps of applying a conductive monomer and then causing a polymerization reaction to form a conductive polymer layer. Further, these steps (1) to (4) may be combined, and a method such as electroplating may be added to further increase the conductivity. Moreover, you may have a heating process after provision of an electroconductive material.

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

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

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

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

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

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

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

(2) A step of applying a metal ion or a metal salt, and then reducing the metal ion or the metal ion in the metal salt to precipitate a metal. , A step of applying a metal ion or metal salt to the graft polymer (metal ion or metal salt applying step), a step of reducing the metal ion or metal ion in the metal salt to precipitate a metal (metal (fine particles)) By performing the film forming step, a conductive film is formed. That is, in the aspect (2), the metal ion such as a hydrophilic group of the graft polymer or the functional group capable of attaching the metal salt adheres (adsorbs) the metal ion or metal salt depending on its function. Subsequently, the adsorbed metal ions and the like are reduced, so that the metal simple substance is deposited over the entire surface of the base material on which the graft polymer is formed, and depending on the precipitation mode, a metal thin film is formed or the metal fine particles are dispersed. Thus, a metal fine particle adhesion layer is formed.

(3) Method of applying electroless plating catalyst or precursor thereof and performing electroless plating In the aspect of (3) of the conductive film forming step in the present invention, the graft polymer comprises an electroless plating catalyst or a precursor thereof. A step of having an interactive group that interacts and applying an electroless plating catalyst or a precursor thereof (electroless plating catalyst application step), and a step of forming a metal thin film by performing electroless plating (electroless) The plating process is performed in order, whereby a conductive film is formed. That is, in the embodiment of (3), the graft polymer having a functional group (that is, a polar group) that interacts with the electroless plating catalyst or its precursor interacts with the electroless plating catalyst or its precursor, A metal thin film is formed by the electroless plating process.

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

The “metal ion or metal salt applying step” and the “metal (fine particle) film forming step” in the aspect (2) will be described in detail.
<Metal ion or metal salt application step>
[Metal ions and metal salts]
A metal ion and a metal salt are demonstrated.
In the present invention, the metal salt is not particularly limited as long as it is dissolved in a suitable solvent to be applied to the graft polymer formation region and can be dissociated into a metal ion and a base (anion). ₃ ) n, MCln, M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom) and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include Ag, Cu, Al, Ni, Co, Fe, and Pd. Ag is preferably used as the conductive film and Co is preferably used as the magnetic film.

[Method of applying metal ions and metal salts]
When applying a method in which the graft polymer has an ionic group and the metal ion is adsorbed to the ionic group when the metal ion or the metal salt is applied to the graft polymer formation region (in the present invention, the entire surface of the insulator layer). For example, the above-mentioned metal salt is dissolved in an appropriate solvent, and the solution containing dissociated metal ions is applied to the substrate surface on which the graft polymer is present, or the substrate having the graft polymer is immersed in the solution. do it. By contacting a solution containing metal ions, metal ions can be ionically adsorbed to the ionic group. From the viewpoint of sufficient adsorption, the metal ion concentration or the metal salt concentration of the solution to be contacted is preferably in the range of 1 to 50% by mass, and more preferably in the range of 10 to 30% by mass. preferable. The contact time is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.

<Metal (fine particle) film formation process>
[Reducing agent]
In the present invention, as a reducing agent used for forming a metal (fine particle) film by reducing a metal salt adsorbed or impregnated into a graft polymer or a metal ion, the used metal salt compound is reduced. And if it has the physical property which deposits a metal, there will be no restriction | limiting in particular, For example, hypophosphite, tetrahydroborate, hydrazine etc. are mentioned.
These reducing agents can be appropriately selected in relation to the metal salt and metal ion to be used. For example, when a silver nitrate aqueous solution or the like is used as the metal salt aqueous solution for supplying the metal ion or metal salt, tetrahydroboron is used. When sodium acid uses an aqueous palladium dichloride solution, hydrazine is preferred.

  As the method for adding the reducing agent, for example, a metal ion or metal salt is imparted to the surface of the substrate on which the graft polymer is present, and then the excess metal salt or metal ion is removed by washing with water. For example, a method of immersing in water and adding a reducing agent thereto, a method of directly applying or dropping a reducing agent aqueous solution having a predetermined concentration on the surface of the substrate, and the like. Moreover, as an addition amount of a reducing agent, it is preferable to use an excessive amount equal to or more than the metal ion, and more preferably 10 times equivalent or more.

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

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

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

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

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

  Next, the “electroless plating catalyst application step” and the “electroless plating step” in the aspect (3) of the conductive material application step of the present invention will be described.

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

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

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

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

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

[Electroless plating]
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
The electroless plating in this step is, for example, after removing the excess electroless plating catalyst (metal) by washing the substrate provided with the electroless plating catalyst obtained in the electroless plating catalyst application step, etc. It is performed by immersing in an electroless plating bath. As the electroless plating bath to be used, a generally known electroless plating bath can be used.
Further, when the substrate to which the electroless plating catalyst precursor is applied is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is attached to or impregnated with the graft polymer, the substrate is washed with water to remove an excess precursor. After removing the body (metal salt, etc.), it is immersed in an electroless plating bath. In this case, reduction of the precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a generally known electroless plating bath can be used as described above.

The composition of a general electroless plating bath is as follows: 1. metal ions for plating, 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath. Among these, copper and gold are particularly preferable from the viewpoint of conductivity.
In addition, there are optimum reducing agents and additives according to the above metals. For example, a copper electroless plating bath contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate, and sodium succinate as complexing agents. It is included. Further, the electroless plating bath of palladium contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

  The film thickness of the conductive film (metal film) thus formed can be controlled by the concentration of the metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, or the like. From the viewpoint of conductivity, the thickness is preferably 0.5 μm or more, and more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

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

<Electroplating process>
In the aspect (3) of the “conductive film forming method” in the present invention, after the electroless plating step, an electroplating step (electroplating step) may be included.
In this step, after electroless plating in the electroless plating step, electroplating can be performed using the metal film (conductive film) formed in this step as an electrode. As a result, a metal film having an arbitrary thickness can be easily formed on a metal film having excellent adhesion to the substrate. By adding this step, the metal film can be formed with a thickness according to the purpose, and the conductive material obtained according to this embodiment is suitable for application to various applications.
As the electroplating method in this embodiment, a conventionally known method can be used. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. From the viewpoint of conductivity, copper, gold, and silver are preferable. More preferred.

  The film thickness of the metal film obtained by electroplating differs depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath, the dipping time, or the current density. In addition, from the viewpoint of conductivity, the film thickness when used for general electric wiring or the like is preferably 0.3 μm or more, and more preferably 3 μm or more.

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

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

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

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

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

In the present invention, the conductive pattern material can be formed by etching the conductive material produced by the conductive material manufacturing method.
[Step of etching metal film to form metal pattern]
As the etching method for forming a metal pattern by etching the metal film on the surface of the conductive material obtained by the present invention, “subtractive method” and “semi-additive method” are used.

"Subtractive method"
The subtractive method is: (1) Applying a resist layer on the metal film created by the above method → (2) Forming resist pattern of conductor to be left by pattern exposure and development → (3) Unnecessary metal by etching Remove film → (4) A method of peeling a resist layer and forming a metal pattern. The thickness of the metal film used in this embodiment is preferably 5 μm or more, and more preferably in the range of 5 to 30 μm.

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

Application method 1. Photosensitive dry film The photosensitive dry film generally has a sandwich structure sandwiched between a polyester film and a polyethylene film, and is pressed with a hot roll while peeling the polyethylene film with a laminator.
2. Liquid resist coating methods include spray coating, roll coating, curtain coating, and dip coating. In order to apply both surfaces simultaneously, roll coating and dip coating are preferable because both surfaces can be coated simultaneously.

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

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

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

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

"Semi-additive method"
The semi-additive method is: (1) coating a resist layer on a metal film formed on a graft polymer → (2) forming a resist pattern of a conductor to be removed by pattern exposure and development → (3) removing the resist by plating. Forming a metal film on the pattern portion → (4) Stripping DFR → (5) A metal pattern forming method of removing an unnecessary metal film by etching. In these steps, the same technique as the “subtractive method” can be used. As the plating method, electroless plating or electroplating described above can be used. In addition, the thickness of the metal film used is preferably about 1 to 3 μm in order to complete the etching process in a short time. Moreover, you may perform electrolytic plating and electroless plating further with respect to the formed metal pattern.
By such an etching method, a conductive pattern material using the conductive material obtained in the present invention can also be obtained. Since the conductive material obtained by the present invention has a highly adhesive metal film formed on a smooth substrate, etching forms a fine metal pattern with high adhesion on a smooth substrate. Useful for forming electrical circuits.

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

  The conductive material obtained by the production method of the present invention is a copper that exhibits high adhesion strength without roughening the surface of heat-resistant, low dielectric constant polymer such as epoxy resin, polyimide resin, liquid crystalline resin, polyarylene resin, etc. Since a stretched substrate can be provided, it is useful as a substrate in the printed wiring board field and the flexible wiring field.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Examples 1-5)
1. Preparation of initiator-containing insulating substrate (specific example 1: formation of an epoxy insulator layer containing an initiator)
As component (A), bisphenol A type epoxy resin (epoxy equivalent 185, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 20 parts by mass (hereinafter, all compounding amounts are expressed in parts by mass), cresol novolac type epoxy resin (epoxy equivalent) 215, 45 parts by Daikoku Ink Chemical Co., Ltd. Epicron N-673), and 30 parts by weight of phenol novolac resin (phenolic hydroxyl group equivalent 105, Phenolite by Dainippon Ink Chemical Co., Ltd.) as component (B) After stirring and dissolving in 20 parts of diglycol acetate and 20 parts of solvent naphtha and cooling to room temperature, cyclohexanone varnish of phenoxy resin consisting of 828 and bisphenol S as component (C) (manufactured by Yuka Shell Epoxy Co., Ltd.) YL6747H30, nonvolatile content 30% by mass, weight average (Particle amount 47000) 30 parts, and (D) component as 2-phenyl-4,5-bis (hydroxymethyl) imidazole 0.8 parts, further finely pulverized silica 2 parts, and silicon-based antifoaming agent 0.5 parts An epoxy resin varnish was prepared.

  Furthermore, 10 parts of the polymerization initiating polymer P synthesized by the following method was added to this mixture, stirred and dissolved to prepare an epoxy resin varnish with an initiator. This epoxy resin varnish was applied onto a SUS substrate using a doctor blade, dried at 100 ° C. for 10 minutes and then dried at 200 ° C. for 5 minutes to obtain a cured epoxy substrate having a thickness of 200 microns. Rz was 0.8 μm.

(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-benzoylbenzyl) dimethyl ammonium bromide 8.1g, 2-Hydroxyethylmethaacrylate 9.9g, isopropymethylmethaylate-2-methyl-1,2-azomethyl-2-methyl-2-azomethyl-2-methyl-1,2 ) A solution of 0.43 g and MFG 30 g was added dropwise over 2.5 hours. Thereafter, the reaction temperature was raised to 80 ° C., and the reaction was further continued for 2 hours to obtain a polymer P having a polymerization initiating group.

(Specific Example 2: Epoxy insulator layer containing initiator)
Liquid bisphenol A type epoxy resin (epoxy equivalent 176, manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 825), triazine structure-containing phenol novolac resin MEK varnish (Dainippon Ink Chemical Co., Ltd., Phenolite LA-7052, Non-volatile content 62%, non-volatile phenolic hydroxyl group equivalent 120) 2 g, phenoxy resin MEK varnish (manufactured by Tohto Kasei Co., Ltd., YP-50EK35, non-volatile content 35%) 10.7 g, 1- (4- (2-hydroxyethyl) phenyl) -2-hydroxy-2-methylpropan-1-one was mixed with 2.3 g, MEK 5.3 g, and 2-ethyl-4-methylimidazole 0.053 g, and completely dissolved by stirring. A varnish-like epoxy resin composition was prepared. The epoxy resin composition was applied onto a polyimide film having a thickness of 128 μm (manufactured by Toray DuPont Co., Ltd., Kapton 500H) using a coating bar so that the thickness after drying was 10 μm, and 170 ° C. for 30 minutes. It was dried to obtain an epoxy insulating substrate containing an initiator. The film thickness was 90 μm and Rz was 0.5 μm.

(Specific Example 3: Epoxy insulator layer containing initiator and polymerizable double bond compound)
70 parts (parts by weight, the same applies hereinafter) of phthalic anhydride modified novolak epoxy acrylate having an acid value of 73 (Nippon Kayaku Co., Ltd., using PCR-1050 (trade name)), acrylonitrile butadiene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd.) , 20 parts of PNR-1H (trade name), 3 parts of alkylphenol resin (made by Hitachi Chemical Co., Ltd., using hitanol 2400 (trade name)), radical photopolymerization initiator (Ciba Geigy, Irgacure 651) 7 parts), 10 parts of aluminum hydroxide (made by Showa Denko KK, using Heidilite H-42M (trade name)) and 40 parts of methyl ethyl ketone were mixed to prepare an insulating layer forming material. This coating solution was applied onto a glass substrate using a rod bar and dried at 110 degrees for 10 minutes. The film thickness was 50 μm and Rz was 0.5 μm.

(Specific example 4: Phenoxy ether insulator layer containing initiator)
183 g of toluene, 50 g of polyphenylene ether resin (PKN4752, trade name manufactured by Nippon GE Plastics Co., Ltd.), 100 g of 2,2-bis (4-cyanatophenyl) propane (Arocy B-10, trade name of Asahi Ciba Co., Ltd.), 9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, trade name, manufactured by Sanko Chemical Co., Ltd.) 28.1 g, manganese naphthenate (Mn content = 6% by weight, Nippon Chemical Industry Co., Ltd.) Co., Ltd.) 0.1% 17% toluene diluted solution, 2,2-bis (4-glycidylphenyl) propane (DER331L, trade name of Dow Chemical Japan Co., Ltd.) 88.3g, (4- (2-hydroxyethyl) phenyl) -2-hydroxy-2-m thylpropan-1-one was added 3.3 g, was adjusted coating liquid was heated and dissolved at 80 ° C.. This coating solution was applied onto a glass substrate using a rod bar and dried at 110 degrees for 10 minutes. The film thickness was 50 μm and Rz was 0.4 μm.

(Specific Example 5: Polyethersulfone Insulator Layer Containing Initiator)
25% acrylate of cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight 2500) dissolved in diethylene glycol dimethyl ether, 70 parts by weight, polyethersulfone, 30 parts by weight, imidazole-based curing agent (product name 2E4MZ- CN) 4 parts by weight, caprorank tontris (acroyloxy) isocyanurate (Toagosei Co., Aronix M325) 10 parts by weight, benzophenone (Tokyo Kasei Co., Ltd.) 5 parts by weight, Michler's ketone (Tokyo Kasei Co., Ltd.) 0.5 parts by weight 20 parts by weight of epoxy resin particles having an average particle size of 0.5 μm. The mixture was stirred while adding an appropriate amount of N-methylpyrrolidone, applied onto a glass plate using a roll coater, and dried at 140 ° C. for 10 minutes. The film thickness was 70 μ and Rz was 0.4 μ.

2. Preparation of laminate film in which graft polymer precursor layer is coated on insulating layer Specific examples prepared by the above method The surfaces of insulating layer substrates 1 to 5 are polymerized without any surface treatment or pretreatment. A liquid composition having the following composition comprising a polymer having an acrylic group as a compound and a carboxyl group as an interactive group (hydrophilic polymer having a polymerizable group in the side chain: P-1, obtained by a synthesis example described later) 1 is applied with a rod bar # 6 and dried at 100 ° C. for 1 minute to provide a graft polymer precursor layer. Laminate films 1 to 5 in which the graft polymer precursor layer is formed on the insulator layer by coating Obtained. The film thicknesses of these laminate films were all in the range of 1.0 to 1.5 μm.

(Liquid composition 1 containing a polymerizable compound)
-Hydrophilic polymer (P-1) having a polymerizable group in the side chain 3.1 g
・ Water 24.6g
1-methoxy-2-propanol 12.3 g

(Synthesis example: Synthesis of polymer P-1 having a double bond)
60 g of polyacrylic acid (average molecular weight 25000, Wako Pure Chemical Industries) and 1.38 g (0.0125 mol) of hydroquinone (Wako Pure Chemical Industries) were placed in a 1 l three-necked flask equipped with a condenser, and N, N-dimethylacetamide (DMAc, Wako Pure Chemical Industries) 700 g was added and stirred at room temperature to obtain a uniform solution. While stirring the solution, 64.6 g (0.416 mol) of 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) was added dropwise. Subsequently, 0.79 g (1.25 × 10 ⁻³ mol) of di-n-butyltin dilaurate (Tokyo Chemical Industry) suspended in 30 g of DMAc was added dropwise. Heated in a 65 degree water bath with stirring. After 5 hours, the heating was stopped and the mixture was naturally cooled to room temperature. The reaction solution had an acid value of 7.105 mmol / g and a solid content of 11.83%.

  300 g of the reaction solution was placed in a beaker and cooled to 5 degrees with an ice bath. While stirring the reaction solution, 41.2 ml of 4N aqueous sodium hydroxide solution was added dropwise over about 1 hour. The temperature of the reaction solution during the dropwise addition was 5 to 11 degrees. After the dropping, the reaction solution was stirred at room temperature for 10 minutes, and the solid content was removed by suction filtration to obtain a brown solution. The solution was reprecipitated with 3 liters of ethyl acetate, and the precipitated solid was collected by filtration. The solid was reslurried overnight with 3 liters of acetone. The solid was filtered off and vacuum dried for 10 hours to obtain a light brown powder P-1. When 1 g of this polymer was dissolved in a mixed solvent of 2 g of water and 1 g of acetonitrile, the pH was 5.56 and the viscosity was 5.74 cps. (Viscosity measured by Toki Sangyo Co., Ltd., RE80 type viscosity system at 28 ° C, using rotor 30XR14) Moreover, the molecular weight by GPC was 30000.

3. Exposure (formation of graft polymer)
Next, the laminated films 1 to 5 in which the graft precursor layer is coated on the insulating layer are subjected to pattern exposure by any of the following methods, and then a cleaning process is performed to form a pattern on the insulating layer. Graft pattern materials 1 to 5 in which a graft polymer was formed in a shape were obtained.
The exposure was performed at room temperature for 1 minute using an exposure machine: an ultraviolet irradiation device (UVX-02516S1LP01, manufactured by USHIO INC.). After the exposure, it was thoroughly washed with pure water.

4). Conductivity imparting to the surface graft materials 1 to 5 of the present invention obtained as described above, a conductive material was imparted by the method described in Table 1 below, among the two methods described below. The conductive materials of Examples 1 to 5 were obtained.
Conductivity imparting method A: Implementation of electroless plating and electrolytic plating steps The surface graft materials 1 to 3 were immersed in a 0.1% by mass aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 hour, and then washed with distilled water. Then, after being immersed in an electroless plating bath having the following composition for 10 minutes, electroplating was carried out for 20 minutes in an electroplating bath having the following composition to prepare copper-clad laminates (conductive materials) of Examples 1 to 3.
<Electroless plating bath components>
・ 0.3 g of copper sulfate
・ Tartaric acid NaK 1.7g
・ Sodium hydroxide 0.7g
・ Formaldehyde 0.2g
・ Water 48g

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

Conductivity imparting method B: adhesion of conductive particles, implementation of electroless plating treatment process The formed graft pattern materials 4 to 5 were immersed in a liquid in which Ag particles having positive charges prepared by the following method were dispersed for 1 hour. Thereafter, it was washed with distilled water. Then, the same plating method as the electroconductive method A was implemented, and the copper clad laminated board [electroconductive material] of Example 4, 5 was produced.
<Method of synthesizing Ag particles having positive charge>
Add 3 g of bis (1,1-trimethylammoniumdecanoylaminoethyl) disulfide to 50 ml of ethanol solution (5 mM) of silver perchlorate, and slowly drop 30 ml of sodium borohydride solution (0.4 M) with vigorous stirring. Ions were reduced to obtain a dispersion of silver particles coated with quaternary ammonium.

Evaluation of conductive materials (surface irregularities)
The surface unevenness of the obtained conductive material was measured with nanopics (Nanopics 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). The results are shown in Table 1 below.
(Measurement of metal film thickness)
The metal film thickness was measured using a DMF cantilever. The results are shown in Table 1 below.
(Adhesion strength evaluation)
A copper plate (thickness: 50 μm) was bonded to the surface of the conductive material on which the metal film was formed with an epoxy adhesive (Araldite, manufactured by Ciba Geigy), dried at 140 ° C. for 4 hours, and then subjected to a 90-degree peeling test based on JIS C6481. went. The peeling apparatus used was a tensile tester AGS-J manufactured by Shimadzu Corporation. The results are shown in Table 1 below.

  As is apparent from Table 1, the conductive material obtained by the production method of the present invention has small surface irregularities, a sufficient thickness on the smooth insulator layer surface, and adhesion to the substrate. It was found that an excellent metal film was formed.

5. Formation of pattern Using the conductive material (copper substrate) obtained in Examples 1 to 5, fine wiring was prepared.
A mask film (a metal pattern portion is an opening, a metal pattern) in which a photosensitive dry film (manufactured by Fuji Photo Film) is laminated on the surface of the conductive material [Examples 1 to 5] and a desired conductor circuit pattern is drawn. The non-formed part was exposed to ultraviolet rays through a mask part), and the image was printed and developed. Next, the portion of the metal film (copper thin film) where the resist was removed was removed using cupric chloride etching solution. Thereafter, the dry film was peeled off to obtain a copper fine pattern. The shape of the pattern was measured.

The formed conductive pattern was evaluated as follows.
(Pattern formability)
The fine line width was measured using an optical microscope (manufactured by Nikon, OPTI PHOTO-2). The results are shown in Table 2 below.
(Adhesion strength evaluation)
A copper plate (thickness: 50 μm) was bonded to the surface of the metal pattern (width: 5 mm) with an epoxy adhesive (Araldite, manufactured by Ciba Geigy), dried at 140 ° C. for 4 hours, and then subjected to a 90-degree peeling experiment based on JIS C6481. went. The peeling apparatus used was a tensile tester AGS-J manufactured by Shimadzu Corporation. The results are shown in Table 2 below.

  As is apparent from Table 2, when the conductive pattern was formed using the conductive material of the present invention, the substrate surface had small irregularities, and the surface of the smooth insulator layer had a fine and high adhesion to the substrate. It was found that wiring could be formed.

Claims (5)

  A surface graft comprising a step of providing an insulating layer containing a polymerization initiator in an insulating resin on a support, and a step of forming a graft polymer directly bonded to the surface of the insulating layer. Material manufacturing method.   A surface graft material produced by the method for producing a surface graft according to claim 1.   A step of providing an insulator layer containing a polymerization initiator in an insulating resin on a support, a step of forming a graft polymer directly bonded to the surface of the insulator layer, and a conductive layer on the graft polymer A method for producing a conductive material, comprising: sequentially.   The electroconductive material produced by the manufacturing method of the electroconductive material of Claim 3.   The electroconductive pattern material obtained by etching the electroconductive material produced by the manufacturing method of the electroconductive material of Claim 3.