JP4606924B2 - Graft pattern material, conductive pattern material and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing a graft pattern material useful for forming a conductive pattern material, and a graft pattern material and a conductive pattern 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 graft pattern material useful for forming fine metal wirings used for metal wiring boards and printed wiring boards.

  As a conventional metal pattern forming method useful in the field of conductive patterns, particularly printed wiring boards, “subtractive method”, “semi-additive method” and “full-additive method” are mainly known. In the subtractive method, a metal layer formed on a substrate is provided with a photosensitive layer that is exposed to irradiation with actinic rays, and this photosensitive layer is imagewise exposed and developed to form a resist image. Is a method of forming a metal pattern by etching and finally removing the resist. In the metal substrate used in this method, in order to provide adhesion between the substrate and the metal layer, the substrate interface has been subjected to uneven treatment to develop adhesion by the anchor effect. As a result, the substrate interface portion of the resulting metal pattern becomes uneven, and there is a problem in that the high frequency characteristics deteriorate when used as an electrical wiring. Further, when forming the metal substrate, there is a problem that a complicated process of treating the substrate with a strong acid such as chromic acid is necessary in order to process the substrate.

  In order to solve this problem, a method has been proposed in which a radically polymerizable compound is grafted on the surface of the substrate to modify the surface, thereby minimizing the unevenness of the substrate and simplifying the substrate processing process. However, in this method, an expensive device (γ-ray generator, electron beam generator) is necessary, and the substrate to be used is a normal one. Since a commercially available plastic substrate is used, there is a problem that the graft polymer is not generated to a sufficient extent, and the adhesion between the substrate and the conductive layer is not sufficient. Furthermore, even if the metal substrate produced by this method is patterned by the subtractive method, there are problems peculiar to the subtractive method. In order to form a metal pattern having a high thin line width by the subtractive method, a so-called over-etching method in which the line width after etching becomes narrower than the line width of the resist pattern is effective. However, if an attempt is made to directly form a fine metal pattern by an over-etching method, line bleeding, blurring, disconnection, etc. are likely to occur. From the viewpoint of forming a good fine metal pattern, a metal pattern of 30 μm or less is formed. Formation is difficult. In addition, the metal film existing in the area other than the pattern portion is removed by the etching process, and there is a lot of waste, and there is a problem in terms of environment and price, such as the cost of processing the metal waste liquid generated by the etching process.

In order to solve the above problem, a metal pattern forming method called a semi-additive method has been proposed. In the semi-additive method, a base substrate layer such as Cr is thinly formed on a substrate by plating or the like, and a resist pattern is formed on the base metal layer. Subsequently, after forming a metal layer such as Cu on the base metal layer in a region other than the resist pattern by plating, a wiring pattern is formed by removing the resist pattern. Further, the metal pattern is formed in a region other than the resist pattern by etching the base metal layer using the wiring pattern as a mask. Since this technique is an etching-less technique, it is easy to form a fine line pattern of 30 μm or less, and because the metal is deposited only at a necessary portion by plating, it is effective in terms of environment and price. However, in this method, it is necessary to process the surface of the substrate in order to provide adhesion between the substrate and the metal pattern. As a result, the substrate interface portion of the resulting metal pattern becomes uneven and is used as electrical wiring. At this time, there is a problem that high-frequency characteristics are deteriorated.
JP 58-196238 A Advanced Materials 2000 No.20 P1481-1494

The purpose of the present invention, which has been made in consideration of the above-mentioned conventional technical problems, is a graft polymer pattern material having excellent adhesion to a substrate on a smooth substrate surface and small irregularities at the interface with the substrate. Another object of the present invention is to provide a graft pattern material useful for forming a conductive pattern and a method for producing the same. Another object of the present invention is to form a conductive pattern that can form a fine conductive pattern without performing an etching process, has excellent adhesion to the substrate, and has small unevenness at the interface with the substrate. Another object of the present invention is to provide a conductive pattern forming method and a conductive pattern material obtained thereby.
The conductive pattern material obtained by the present invention is a fine pattern excellent in high-frequency characteristics, and is useful as a conductive layer of a printed wiring board.

As a result of intensive studies, the present inventor has found that the above problem can be solved by providing a graft polymer layer in a pattern 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 insulating layer containing a polymerization initiator in an insulating resin, which is a mixture of a thermosetting resin and a thermoplastic resin, on the support, and the surface of the insulating layer is polymerizable. forming a graft polymer directly bonded to the insulator layer surface by contacting the hydrophilic polymer pattern exposure with an unsaturated group in a pattern, sequentially have a, the thermosetting resin is an epoxy resin And a method for producing a graft pattern , wherein the thermoplastic resin is at least one selected from phenoxy resin, polyethersulfone and polyphenylene ether .
< 2 > A graft pattern material produced by the method for producing a graft pattern according to <1> .
< 3 > A step of providing an insulator layer containing a polymerization initiator in an insulating resin, which is a mixture of a thermosetting resin and a thermoplastic resin, on the support, polymerizable unsaturated unsaturated on the surface of the insulator layer Forming a graft polymer directly bonded to the surface of the insulator layer in a pattern by contacting a hydrophilic polymer having a group with pattern exposure , and providing a conductive layer on the graft polymer pattern. sequentially closed, the thermosetting resin is at least one selected from an epoxy resin and an isocyanate resin, said thermoplastic resin is at least one selected from phenoxy resins, polyether sulfones and polyphenylene ether The manufacturing method of the electroconductive pattern characterized by these.
< 4 > A conductive pattern material produced by the method for producing a conductive pattern according to < 3 >.

ADVANTAGE OF THE INVENTION According to this invention, the graft polymer pattern material which is excellent in adhesiveness with a board | substrate on the smooth board | substrate surface, and has small unevenness | corrugation in the interface with a board | substrate, and its manufacturing method can be provided.
In addition, according to the present invention, it is possible to form a fine conductive pattern without performing an etching step, and to form a conductive pattern that has excellent adhesion to the substrate and has small irregularities at the interface with the substrate. The conductive pattern forming method and the conductive pattern material obtained thereby can be provided.
The conductive pattern material obtained by the present invention is a fine pattern excellent in high-frequency characteristics, and is useful as a conductive layer of a printed wiring board.

In the method for producing a surface graft material of the present invention, first, an insulating layer containing a polymerization initiator in an insulating resin that is a mixture of a thermosetting resin and a thermoplastic resin is formed on an arbitrary support. After that, surface graft polymerization is carried out in a pattern shape using the polymerization initiator contained in the insulator layer as a base point to form a graft polymer pattern directly bonded to the surface of the insulating resin layer.
In the present invention, an insulating resin that is a mixture of a thermosetting resin and a thermoplastic resin is characterized by including a polymerization initiator and providing an initiator-containing insulator layer. An insulating layer made of an insulating resin material having desired characteristics and having a polymerization initiating ability can be formed on the surface of the support. After that, by applying energy such as exposure to only a desired portion of the surface of the formed insulator layer, by forming a graft polymer directly bonded to the insulator layer in a pattern only in that region, it is smooth, Graft pattern materials can be made to which any material can be deposited. By attaching a conductive material to the graft polymer in this graft pattern material, a fine conductive pattern with excellent adhesion can be formed even on a smooth and uniform substrate.

In the present invention, by including a polymerization initiator in an insulating resin that is a mixture of a thermosetting resin and a thermoplastic resin, the adhesion between the insulating layer and the graft polymer formed in a pattern becomes stronger. Strong adhesion is expressed.
The reason for this is not clear, but the density of the graft polymer formed by adding a polymerization initiator to the insulating resin layer is increased, and the interaction with the conductive material is further increased, resulting in improved adhesion. It is done.
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 the insulating resin in the present invention, to use a mixture of thermosetting resin and thermoplastic resin. In the present invention forms an insulating layer used in which a photopolymerization initiator to these absolute Sophora fat. 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 resin, an isocyanate resin, and the like in the present invention as a thermosetting resin. It is necessary to use at least one selected from epoxy resins and isocyanate resins .
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.

As the thermoplastic resin, for example, phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenylene ether, polyether imide and the like, in the present invention, as the thermoplastic resin, phenoxy resin, poly It is necessary to use at least one of ether sulfone and polyphenylene ether . 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).

(Mixture of thermoplastic resin and thermosetting resin)
As the insulating resin in the present invention , a mixture of a thermoplastic resin and a thermosetting resin is used . 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)
Also it can be added the desired compound in accordance with the purpose of the application in the insulator layer. 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. Acrylate compounds usable in the present invention [(meth) acrylate] may be any one having an acryloyl group is an ethylenically unsaturated group in the molecule is not particularly limited, curable, formed of the insulator layer From the viewpoint of improving hardness and 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 insulator 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 the insulator layer component in 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 amount 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 generally it is about 0.1 to 50% by mass as a solid content in the insulating layer. It is preferable that it is about 1.0-30.0 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 hardly proceeds.

(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 a graft polymer directly bonded to the surface of the insulator layer in a pattern]
In order to form a graft polymer directly bonded to the surface of the insulating layer thus formed in a pattern, a compound having an unsaturated double bond capable of radical polymerization is brought into contact with the surface of the insulating layer. The pattern exposure method may be used. 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 method of forming a graft pattern of the present invention, the polymerizable compound to be used can be arbitrarily used as long as it has a “radical polymerizable unsaturated double bond” necessary for bonding to the insulator layer. For example, in the conductive pattern forming method according to the second aspect of the present invention, in addition to the “unsaturated double bond capable of radical polymerization”, a conductive material described later is required to adhere to the graft polymer. It is preferable to use a polymerizable compound further having a “functional group capable of interacting with a conductive material”.
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.

The polymerizable compound having an unsaturated double bond capable of radical polymerization, which is an essential requirement of the present invention, and optionally having a functional group capable of interacting with a conductive material is a polymer and has an average molecular weight. Is selected in the range of 1000 to 500,000. Such a polymer can be obtained by methods such as addition polymerization such as normal radical polymerization and anionic polymerization, and polycondensation.

Specifically, in the present invention, 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 having a hydrophilic group that is a polar group is used .

-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 pattern on insulating layer surface)
By exposing the graft precursor layer formed on the insulating layer as described above in a pattern, radicals are generated in the exposed region of the precursor layer, and react with the adjacent graft precursor layer to cause the insulating layer. / A strong chemical bond occurs at the precursor layer interface, and a graft polymer pattern is formed only in the exposed area.
(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.
Lasers include gas lasers such as carbon dioxide lasers, nitrogen lasers, Ar lasers, He / Ne lasers, He / Cd lasers, Kr lasers, solid state lasers such as liquid (pigment) lasers, ruby lasers, Nd / YAG lasers, GaAs / An excimer laser such as GaAlAs, InGaAs laser, various blue semiconductor lasers, KrF laser, XeCl laser, XeF laser, Ar ₂ or the like can be used. In particular, exposure with a solid-state high-power infrared laser such as a semiconductor laser or a YAG laser that emits infrared light having a wavelength of 700 to 1200 nm is preferable.
Further, when performing high-resolution pattern exposure, stepper exposure such as an i-line stepper, KrF stepper, and ArF stepper can also be used.

  Pattern exposure can be performed via a mask pattern using a parallel light source, but from the viewpoint of efficiently forming a desired pattern, pattern exposure using digital data can be performed using beam light. Preferably, according to this exposure method, a fine graft pattern corresponding to the accuracy of the exposure light source can be easily formed.

Various functional pattern materials can be obtained by attaching various materials to the graft pattern thus obtained by the functional group to be introduced. The method of the present invention is useful for forming the pattern, and the conductive pattern obtained by this method is excellent in adhesion to a smooth insulator layer and can form a fine conductive pattern.
[Process for imparting conductive material to graft pattern directly bonded to insulator layer surface]
Steps for imparting conductivity to the graft polymer pattern include (1) a step of attaching conductive fine particles to the graft polymer formed in a pattern, and (2) a metal ion or a metal salt added to the graft polymer formed in a pattern. Thereafter, a step of reducing the metal ions or metal ions in the metal salt to deposit a metal, and (3) applying an electroless plating catalyst or a precursor thereof to the graft polymer formed in a pattern, It is one selected from a step of performing plating, and a step of (4) applying a conductive monomer to the pattern-formed graft polymer and then causing a polymerization reaction to form a conductive polymer layer. It is preferable. Further, these steps (1) to (4) may be combined, and in order to further increase the conductivity, a method such as electroplating may be further added to the formed conductive pattern material. Moreover, you may have a heating process after provision of an electroconductive raw 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 formed in the pattern. The conductive fine particles exemplified below are electrostatically, What is necessary is just to make it adhere (adsorb | suck) to a polar group ionically.

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 a metal salt to the patterned graft polymer (metal ion or metal salt applying step), a step of reducing the metal ion or metal ion in the metal salt to deposit a metal (metal) By performing the (fine particle) film forming step), a conductive pattern 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. Then, the adsorbed metal ions and the like are reduced, so that the metal simple substance is deposited in the graft polymer formation region, and depending on the deposition mode, a metal thin film is formed or a metal fine particle adhesion layer formed by dispersing metal fine particles is formed. Will be 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, The metal thin film is formed only in the region where the graft polymer is formed by the electroless plating process.

  As a result, a metal (fine particle) film is formed in a pattern, 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 a metal ion or a metal salt is applied to the graft polymer formation region, when the graft polymer has an ionic group and a method of adsorbing the metal ion to the ionic group is used, the above metal salt is used in an appropriate solvent. The solution containing the metal ions dissolved and dissociated in (1) is applied to the surface of the substrate formed by forming the graft polymer in a pattern, or the substrate formed by forming the graft polymer in the pattern 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, the metal salt present by adsorbing or impregnating the graft pattern, or the reducing agent used to reduce the metal ions and form a metal (fine particle) film, 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 pattern exists, and then washed with water to remove excess metal salt or metal ion, and the substrate is subjected to ion exchange 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 substrate surface, 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 formed into a pattern has a functional group having a negative charge, a metal ion having a positive charge is adsorbed here, and the adsorbed metal ion is reduced to reduce the amount of the metal (metal) A region where a thin film or metal fine particles) is deposited 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 by 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 (graft polymer layer) formed in a pattern. The The size of the metal fine particles to be produced is about 1 μm to 1 nm in particle size.

The conductive film produced by the above method may be used as it is when the metal fine particles are densely adsorbed and apparently form a metal thin film, but from the viewpoint of ensuring efficient conductivity. It is preferable to further heat-treat the formed pattern.
The heating temperature in the heat treatment step is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably about 200 ° C. The heating temperature is preferably 400 ° C. or lower in consideration of the processing efficiency 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 substance application step” in 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 formed in a pattern.

[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 substrate surface on which the graft polymer is present, or the substrate having the graft polymer is immersed in the solution. By contacting a solution containing a metal ion, 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 having a pattern according to the pattern of the graft polymer layer is obtained by performing electroless plating on the substrate to which the electroless plating catalyst or the like has been applied from the electroless plating catalyst or the like application step. Metal film) is formed. That is, by performing electroless plating in this step, a high-density conductive film (metal film) is selectively formed on the graft pattern obtained by the above step. The formed conductive film (metal pattern) 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 patterned conductive film (metal pattern) formed in this way is controlled by the concentration of metal salt or metal ion in the plating bath, the immersion time in the plating bath, or the temperature of the plating bath. However, from the viewpoint of conductivity, it is preferably 0.5 μm or more, and more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

  In the formation region of the patterned conductive film (metal pattern) obtained as described above, electroless plating catalyst and fine particles of plating metal are packed in the surface graft film (graft pattern) by cross-sectional observation by SEM. It was confirmed that the particles were dispersed and relatively large particles were deposited thereon. 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 pattern forming method” in the present invention, the electroless plating step may be followed by an electroplating step (electroplating step).
In this step, after electroless plating in the electroless plating step, electroplating can be performed using the conductivity (metal pattern) formed in this step as an electrode. As a result, a metal film having an arbitrary thickness can be easily formed on a metal pattern having excellent adhesion to the glass substrate. By adding this step, the metal film can be formed with a thickness according to the purpose, and the conductive pattern 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, for example, by performing electroplating in addition to forming a patterned metal film with a thickness according to the purpose. It can also be done for purposes such as The plating performed for this purpose is selected from the group consisting of nickel, palladium, gold, silver, tin, solder, rhodium, platinum, and compounds thereof on the conductive film or metal pattern surface formed of copper or the like. It can be performed using the material to be used.

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 interacting group, particularly preferably the ionic group, of the graft pattern, and then remains as it is. In this method, a polymerization reaction is caused to form a patterned conductive polymer layer. By this method, a patterned conductive layer made of a conductive polymer is formed.
Here, the patterned conductive layer made of the conductive polymer is formed by polymerizing the grafted polymer interactive group and the conductive monomer ionically adsorbed, so that it has excellent adhesion and durability with the substrate, By adjusting the polymerization reaction conditions such as the monomer supply rate, the film thickness and conductivity can be controlled.

Although there is no restriction | limiting in particular in the method of forming such a patterned conductive polymer layer, From the viewpoint that a uniform thin film can be formed, it is preferable to use the method described below.
First, the substrate on which the graft polymer is formed in a pattern 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. A monomer capable of forming a conductive polymer, 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 a very thin film of conductive polymer is formed on the surface of the graft polymer generation region formed in a pattern 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.

As described above, by providing a conductive material to the graft polymer generation region of the graft pattern material obtained by the graft pattern manufacturing method of the present invention, the conductive material having a high-definition conductive pattern corresponding to the graft pattern. Pattern material can be obtained. 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 pattern exhibiting high adhesion strength, for example, a substrate having an insulator layer on which high-definition wiring made of copper is formed, can be suitably used for a printed wiring board or the like.
According to the manufacturing method of the present invention, it is possible to easily form a conductive pattern formed of a conductive material such as a copper wiring having a fineness of 20 microns or less and high adhesion strength, which has been difficult with the prior art. It becomes possible.

  The conductive pattern material obtained by the production method of the present invention 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. And since it becomes a board | substrate which has an insulator layer in which metal patterns, such as a high-definition copper wiring, were formed, it can apply suitably for the printed wiring board field | area and the flexible wiring field | area.

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 example prepared by the above method: polymerization is performed on the surfaces of insulating layer substrates 1 to 5 without performing surface treatment or pretreatment, respectively. Liquid composition having the following composition comprising a polymer having an acrylic group as a functional 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) The product 1 was applied with a rod bar # 6 and dried at 100 ° C. for 1 minute to provide a graft polymer precursor layer, and the laminated film 1-5 in which the graft polymer precursor layer was formed on the insulator layer by coating Got. The film thicknesses of these laminate films were all in the range of 1.0 to 1.5 μm. Table 1 below shows which substrate was used.

(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 the method described in Table 1 below among the three exposure methods shown below, and the cleaning treatment is performed. 1-5 of the surface graft material in which the graft polymer was formed on the insulator layer was obtained.
(Exposure method 1)
A mask pattern (NC-1 Toppan Printing Co., Ltd.) on which chromium was vapor-deposited was overlaid on the laminate film, and exposed from above with an exposure machine (UVX-02516S1LP01, manufactured by Ushio Inc.) for 1 minute. After the exposure, it was thoroughly washed with pure water.
(Exposure method 2)
A mask pattern (NC-1 Toppan Printing Co., Ltd.) on which chromium is vapor-deposited is overlaid on the laminate film and irradiated with UV light from above (400 W high-pressure mercury lamp: UVL-400P, manufactured by Riko Kagaku Sangyo Co., Ltd., irradiation time 5) Min). After the light irradiation, the mask was removed and washed with water to obtain a graft pattern material grafted in a pattern.
(Exposure method 3)
The laminated film was exposed imagewise with a laser emitting blue light having a wavelength of 405 nm (beam diameter 20 μm) and washed with water to obtain a graft pattern material grafted in a pattern.

4). Conductivity imparting to the graft pattern 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 three methods described below, and carried out. The conductive pattern materials of Examples 1 to 5 were obtained.
Conductivity imparting method A: Implementation of electroless plating step The graft pattern material 1 was immersed in a 0.1% by mass aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 hour, and then washed with distilled water. Then, the electroconductive pattern material of Example 1 was produced by immersing in an electroless plating bath having the following composition for 60 minutes.
<Electroless plating bath components>
・ OPC Kappa-H T1 (Okuno Pharmaceutical Co., Ltd.) 6mL
・ OPC Kappa-H T2 (Okuno Pharmaceutical Co., Ltd.) 1.2mL
・ OPC Kappa-H T3 (Okuno Pharmaceutical Co., Ltd.) 10mL
・ Water 83mL

Conductivity imparting method B: implementation of electroless plating and electrolytic plating steps The graft pattern materials 2 to 4 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 15 minutes in an electroplating bath having the following composition to produce conductive pattern materials of Examples 2 to 4.
<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 C: Conductive particle adhesion, implementation of electroless plating treatment step After the formed graft pattern material 5 is immersed in a liquid in which Ag particles having positive charges prepared by the following method are dispersed, for 1 hour, Washed with distilled water. Then, the same plating method as the conductive method B was implemented, and the conductive pattern material of Example 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 (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.
(Surface unevenness)
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 2 below.
(Measurement of metal film thickness)
The metal film thickness was measured using a DMF cantilever. The results are shown in Table 2 below.
(Adhesion strength evaluation)
A metal pattern (width 5 mm) is formed, a copper plate (thickness: 50 μm) is bonded to the surface of the metal pattern with an epoxy adhesive (Araldite, manufactured by Ciba Geigy), dried at 140 ° C. for 4 hours, and then based on JIS C6481 A 90 degree peeling experiment was conducted. 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, according to the method for producing a conductive pattern material of the present invention, the unevenness of the surface is small, the surface of the smooth insulator layer has a sufficient thickness, and excellent adhesion to the substrate. It was found that fine wiring (metal film pattern) can be formed. In addition, the obtained conductive pattern material has fine metal wiring corresponding to the exposure pattern and is excellent not only in adhesion but also in smoothness. ) Is useful.

Claims (4)

A step of providing an insulating layer containing a polymerization initiator in an insulating resin, which is a mixture of a thermosetting resin and a thermoplastic resin, on the support; and a polymerizable unsaturated group on the surface of the insulating layer the with contacting the hydrophilic polymer to form a direct bond graft polymer insulator layer surface in a pattern by pattern exposure, sequentially have a, the thermosetting resin is an epoxy resin and an isocyanate A method for producing a graft pattern, which is at least one selected from resins, and wherein the thermoplastic resin is at least one selected from phenoxy resins, polyether sulfones and polyphenylene ethers . A graft pattern material produced by the method for producing a graft pattern according to claim 1 . A step of providing an insulator layer containing a polymerization initiator in an insulating resin, which is a mixture of a thermosetting resin and a thermoplastic resin, on the support, and having a polymerizable unsaturated group on the surface of the insulator layer forming a direct bond graft polymer insulator layer surface in a pattern by contacting pattern exposure hydrophilic polymer, and a step of providing a conductive layer on the graft polymer pattern, sequentially have a The thermosetting resin is at least one selected from an epoxy resin and an isocyanate resin, and the thermoplastic resin is at least one selected from a phenoxy resin, a polyethersulfone, and a polyphenylene ether. A method for producing a conductive pattern. The electroconductive pattern material produced by the manufacturing method of the electroconductive pattern of Claim 3 .