JP2006104045A - Conductive glass substrate, method of forming conductive glass substrate, and method of forming conductive pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive glass substrate obtained by forming a conductive film having excellent adhesion to a glass substrate and having optional conductivity, a method of forming the same and a method of forming a conductive pattern which is suitable for making out a material necessary for the formation of highly conductive and optional pattern formed using the conductive glass substrate or using a method same as that for the conductive glass substrate. <P>SOLUTION: The conductive glass substrate is formed by bringing a radically polymerizable unsaturated compound into contact with the glass substrate having a surface bonded with a compound having a polymerization initiating part capable of initiating radical polymerization by photo-cleavage and a base material bonding part, imparting energy to form a graft polymer on the glass substrate and applying a conductive material on the graft polymer formed area. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a conductive glass substrate, a method for forming the same, and a method for forming a conductive pattern. More specifically, a conductive film such as silver or copper having high density and excellent durability and productivity is applied to the glass substrate. The present invention relates to a conductive glass substrate formed and a simple formation method thereof, and a conductive pattern formation method useful for forming an electric wiring material, an electromagnetic wave prevention film, a magnetic film and the like using the conductive glass substrate.

Conventionally, various conductive substrates are used for forming a wiring substrate. A typical example of these is a conductive substrate in which a thin film conductive material formed by a known method such as vacuum deposition is provided on an insulator. Among these, a conductive glass substrate obtained by using glass as a substrate and laminating a conductive substance such as copper or ITO on the glass substrate is useful as an electric wiring substrate such as a flat panel display element.
As a method of forming a wiring substrate using these conductive glass substrates as a material, a resist is applied on the conductive film, a part of the resist prepared in advance is removed by pattern exposure, and then an etching process is performed to obtain a desired one. A method of forming a pattern is a general method (see, for example, Patent Document 1).
Wiring on the glass substrate thus prepared is useful for various applications, and is used for wiring of flat panel display elements, for example, bus electrodes and address electrodes in PDP display elements. Further, in a liquid crystal display element, it is used for a wiring pattern for mounting a driving IC by a COG (chip on glass) method on a transparent electrode or a glass substrate on which the liquid crystal display element is formed.
Among these conductive glass substrates, a conductive substrate formed by depositing an ITO layer on a glass substrate has good conductivity, and, as another effect, has high transparency and suitability for processing such as etching. Widely used as a transparent electrode because it is good. However, since the ITO layer is formed by vapor deposition, it is difficult to increase the film thickness. When the film thickness is small, the electric resistance increases and a large amount of current cannot flow, which limits the application. there were.
In addition, when trying to form a conductive film made of a metal other than ITO, metals such as gold, platinum, and copper used as conductive materials have low adhesion to the glass substrate of the resulting metal film. A method has been adopted in which a chromium vapor deposition film is formed on a substrate and the metal thin film is formed on the chromium vapor deposition film. In this method, when a desired metal film is produced, a chromium vapor deposition operation is required, which is not preferable in terms of process and cost. Therefore, there has been a demand for a conductive glass substrate in which a metal film such as gold, platinum, or copper is formed on the glass substrate surface with high adhesion without forming a chromium vapor deposition film.
In any case, since the conductive film of the conductive glass substrate is formed by vapor deposition, the film thickness obtained is limited, and it is difficult to obtain desired conductivity. There is a strong desire for a method of forming a conductive film having the following.
JP 2004-31588 A

An object of the present invention is to solve the conventional problems of the present invention and achieve the following objects.
That is, the object of the present invention is to provide a conductive glass substrate formed by forming a conductive film having an arbitrary conductivity and an excellent conductivity with a glass substrate, and an excellent conductivity with the substrate. It is an object of the present invention to provide a method for forming a conductive glass substrate that can easily form a conductive film on the glass substrate.
Another object of the present invention is to have high conductivity and arbitrary pattern formation using a conductive glass substrate that is excellent in adhesion to a glass substrate and has a conductive film having arbitrary conductivity. It is an object of the present invention to provide a method for forming a conductive pattern suitable for producing the material.

As a result of investigation, the present inventors can solve the above-mentioned nuclear problem by bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a substrate binding site to the glass substrate surface. The present invention has been completed.
That is, the conductive glass substrate of the present invention is characterized in that a conductive substance is added to the graft polymer that is directly chemically bonded to the glass substrate.
The conductive glass substrate according to claim 2 is capable of radical polymerization on a glass substrate formed by bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a base material binding site to the surface. It is characterized in that an unsaturated compound is brought into contact and energy is applied to form a graft polymer on the glass substrate, and then a conductive material is applied to the graft polymer generation region.
Here, the conductive material is applied by (1) a method of attaching conductive fine particles, (2) applying a metal ion or metal salt, and then reducing the metal ion or metal ion in the metal salt. A method of depositing a metal, (3) a method of applying an electroless plating catalyst or a precursor thereof to perform electroless plating, and (4) a conductive polymer layer by applying a conductive monomer and causing a polymerization reaction. It is a preferable aspect that it is made by any method selected from the method of forming.
Moreover, a conductive pattern material can be formed by etching the conductive film on the surface of the conductive glass substrate of the present invention.

  According to a sixth aspect of the present invention, there is provided a method for forming a conductive glass substrate, comprising: bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a base material binding site to a glass substrate; A radical-polymerizable unsaturated compound is brought into contact, energy is imparted, and radicals are generated from the compound having a polymerization initiation site and a substrate-binding site capable of initiating radical polymerization by the photocleavage, and the radical is initiated. And a step of forming a graft polymer formed by bonding to a glass substrate, and a step of forming a conductive film by adding a conductive substance to the generated graft polymer.

In the conductive pattern forming method according to claim 11 of the present invention, a step of bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a base material binding site to a glass substrate, An unsaturated compound capable of radical polymerization is brought into contact and exposed in a pattern to form a graft polymer generation region and a non-generation region; and a conductive material is applied to the graft polymer generation region to form a conductive film. And a surface resistance value of the obtained conductive film is 0.1 to 20Ω / □.
The pattern exposure in the step of forming the graft polymer generation region and the non-generation region may be pattern exposure using a mask pattern or pattern exposure by laser scanning exposure.

The polymerization initiation site in the compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a substrate binding site used here is a C—C bond, a C—N bond, a C—O bond, or a C—Cl bond. It is a preferable aspect that includes any one selected from the group consisting of N—O bond and S—N bond.
In addition, the step of forming a conductive film by applying a conductive substance to the generated graft polymer includes (1) a step of attaching conductive fine particles to the generated graft polymer, and (2) a metal ion or metal to the generated graft polymer. A step of applying a salt and then reducing the metal ions or the metal ions in the metal salt to deposit a metal; (3) applying an electroless plating catalyst or a precursor thereof to the resulting graft polymer; It is preferably any one selected from a step of performing plating and (4) a step of providing a conductive monomer and then causing a polymerization reaction to form a conductive polymer layer.
Moreover, (2) When implementing the process which reduces the metal ion in metal salt and precipitates a metal, you may have a heating process further after that.

  In the conductive glass substrate of the present invention, a conductive material is imparted to the graft polymer directly bonded to the glass substrate, so that a continuous conductive thin film or conductive material fine particles are dispersed and adhere to the graft polymer. The conductive film thus formed has high strength and wear resistance due to the strong adhesion to the glass substrate due to the function of the graft polymer. In addition, since the conductive material can be arbitrarily applied to the graft polymer by the preferred method, a desired conductive material can be applied to the glass substrate surface, and the conductive material applied to the conductive film Desired conductivity can be realized by controlling the amount of adhesion and the film thickness of the continuous conductive film.

  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 (2-3) A method of impregnating a hydrophilic graft polymer with a solution containing a metal salt or a solution in which the metal salt is dissolved By taking the method of (2-3), a necessary metal ion or metal salt can be provided even if the compound forming the hydrophilic graft polymer has a positive charge. it can.

(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.
In any of the above embodiments, when applying the conductive material, (3) when performing a step including electroless plating, it is preferable to use an electroless plating bath containing trialkanolamine. More preferably, an electroless plating bath is used.
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.

The graft polymer in the present invention is extremely strongly fixed to the glass substrate by chemically bonding to a compound having a polymerization initiation site and a base material binding site bonded to the glass substrate surface at one end. In addition, it is characterized in that it is fixed to the glass substrate only at one end of the polymer and is free from the other end, so that the polymer is less constrained and has extremely high mobility.
For this reason, the graft polymer in the present invention is a high-strength graft polymer even if it is a thin layer. In addition, a functional group that interacts with the conductive material is introduced into the side chain of the graft polymer, and when conductive fine particles, metal salts, and the like are ionically attached (adsorbed) to the functional group, the conductive group Since the material is firmly fixed, it is considered that a high-strength conductive film (conductive layer) excellent in adhesion to the glass substrate is formed. In addition, the process of generating a graft polymer on the surface of the glass substrate is performed by sequentially applying a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a base material binding site, an unsaturated compound capable of radical polymerization, and the like. Such a conductive glass substrate can be easily formed without requiring an expensive apparatus such as chromium vapor deposition, which is possible by a simple method such as heat drying and / or applying energy such as light irradiation. . The method for forming a conductive glass substrate of the present invention can be applied not only to a glass substrate but also to an ITO substrate formed by depositing ITO on glass.

  In the present invention, since the graft polymer has extremely high mobility as described above, the adhesion (adsorption) rate is extremely high compared with the case where a metal is adsorbed to a general crosslinked polymer film. The amount of metal that can be adsorbed per area increases. For this reason, the amount of adsorbed metal is controlled so as to form a continuous metal thin film layer, or a continuous metal layer is formed by fusing adjacent metal particles by heating a dense metal particle adhesion layer. In such a case, a fine wiring pattern can be formed, and if such a wiring is formed, conductivity is not hindered or disconnected by a gap existing between the metals.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in adhesiveness with a glass substrate, and is excellent in adhesiveness with a conductive glass substrate formed by forming the electrically conductive film which has arbitrary electroconductivity, and arbitrary electroconductivity. The conductive glass substrate forming method which can form the electrically conductive film which has it on a glass substrate easily can be provided.
Moreover, according to this invention, it is excellent in adhesiveness with a glass substrate, and requires high electroconductivity and arbitrary pattern formation using the electroconductive glass substrate formed by forming the electrically conductive film which has arbitrary electroconductivity. A conductive pattern forming method suitable for manufacturing a material can be provided.

Hereinafter, the present invention will be described in detail.
The conductive glass substrate of the present invention is characterized in that a conductive material is added to a graft polymer that is directly chemically bonded to the glass substrate. Hereinafter, the configuration of the conductive glass substrate will be described in order according to the steps of the forming method.
In detail, the conductive glass substrate of the present invention is capable of radical polymerization on a glass substrate formed by bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a base material binding site to the surface. It is characterized in that an unsaturated compound is brought into contact and energy is applied to form a graft polymer on the glass substrate, and then a conductive material is applied to the graft polymer generation region. Such a conductive glass substrate can be obtained by the following forming method.
That is, (A) a step of bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a base material binding site to a glass substrate (hereinafter referred to as “photocleavable compound binding step” as appropriate). (B) A radical from a compound having a polymerization initiation site and a base material binding site capable of initiating radical polymerization by photocleavage by bringing an unsaturated compound capable of radical polymerization into contact with the glass substrate to impart energy. And a step of producing a graft polymer obtained by bonding it to a glass substrate using the same as a starting species (hereinafter, referred to as “graft polymer production step” as appropriate), and (C) a conductive substance in the produced graft polymer. And a step of forming a conductive film (hereinafter referred to as a conductive film formation step).

  Further, in the present invention, the (C) conductive film forming step specifically includes (1) a step of attaching conductive fine particles to the produced graft polymer (“conductive fine particle attachment step”), (2) A metal ion or metal salt is imparted to the resulting graft polymer (“metal ion or metal salt imparting step”), and then the metal ion or metal ion in the metal salt is reduced to precipitate a metal (“metal ( (Fine particle) film forming step)), (3) applying the electroless plating catalyst or precursor thereof to the generated graft polymer (“electroless plating catalyst applying step”), and performing electroless plating (“electroless plating”) Process "), and (4) applying a conductive monomer (" conductive monomer application process ") and causing a polymerization reaction to form a conductive polymer layer (" conductive polymer formation process "), Z It is preferably carried out by either.

<Photocleavable compound binding step and graft polymer forming step>
First, an outline from the photocleavable compound bonding step to the graft polymer production step in the present invention will be described.
The functional group (Z) is present on the glass substrate surface from the beginning. Here, a compound (QY) having a substrate binding site (Q) and a polymerization initiation site (Y) capable of initiating radical polymerization by photocleavage is imparted and brought into contact with the glass substrate surface. As a result, the functional group (Z) present on the glass substrate surface and the base material binding site (Q) are bonded, and the compound (QY) is introduced into the glass substrate surface [photocleavable compound bonding step. ]. Then, the whole surface exposure which gives energy is performed in the state which contacted well-known graft polymer raw materials (unsaturated compound which can be radically polymerized), such as a monomer. Thereby, a graft polymer is produced from the polymerization initiation site (Y) of the compound (QY) over the entire surface of the glass substrate [graft polymer production step].

Hereinafter, each of these steps will be specifically described.
Specific examples of the functional group (Z) present on the substrate surface include a hydroxyl group. These functional groups are originally present on the surface of the glass substrate due to the material of the base material in the glass substrate.

Next, the structure of a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage (hereinafter simply referred to as polymerization initiation site) and a substrate binding site will be specifically described. If this compound is described in detail using a model of the compound (QY) having a substrate binding site (Q) and a polymerization initiation site (Y), in general, the polymerization initiation site (Y) is: It is a structure containing a single bond that can be cleaved by light.
As the single bond that is cleaved by this light, carbonyl α-cleavage, β-cleavage reaction, light-free rearrangement reaction, phenacyl ester cleavage reaction, sulfonimide cleavage reaction, sulfonyl ester cleavage reaction, N-hydroxysulfonyl ester cleavage reaction, benzyl Examples thereof include a single bond that can be cleaved using an imide cleavage reaction, a cleavage reaction of an active halogen compound, and the like. These reactions break a single bond that can be cleaved by light. Examples of the single bond that can be cleaved include a C—C bond, a C—N bond, a C—O bond, a C—Cl bond, a N—O bond, and a S—N bond.

  In addition, since the polymerization initiation site (Y) containing a single bond that can be cleaved by light is the starting point of graft polymerization in the graft polymer production step, when the single bond that can be cleaved by light is cleaved, the cleavage reaction causes Has the function of generating radicals. As described above, examples of the structure of the polymerization initiation site (Y) having a single bond that can be cleaved by light and capable of generating radicals include structures containing the following groups.

  Aromatic ketone groups, phenacyl ester groups, sulfonimide groups, sulfonyl ester groups, N-hydroxysulfonyl ester groups, benzylimide groups, trichloromethyl groups, benzyl chloride groups, and the like can be mentioned.

  When such a polymerization initiation site (Y) is cleaved by exposure and a radical is generated, if there is a polymerizable compound in the vicinity of the radical, this radical functions as a starting point for the graft polymerization reaction. The graft polymer can be produced.

  The substrate binding site (Q) is composed of a reactive group capable of reacting with and binding to the functional group Z present on the glass substrate surface. Specifically, the reactive group is as shown below. Groups.

  The polymerization initiation site (Y) and the substrate binding site (Q) may be directly bonded or may be bonded via a linking group. Examples of the linking group include a linking group containing an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur. Specifically, for example, a saturated carbon group, an aromatic group, an ester group, an amide group. Ureido group, ether group, amino group, sulfonamide group, and the like. The linking group may further have a substituent, and examples of the substituent that can be introduced include an alkyl group, an alkoxy group, and a halogen atom.

  Specific examples [Exemplary Compound 1 to Exemplified Compound 16] of Compound (QY) having a substrate binding site (Q) and a polymerization initiation site (Y) are shown below together with the cleavage portion. For example, a known silane coupling agent containing a single bond that can be cleaved by light as described above can be suitably used.

The photocleavable compound bonding step in the present invention is a step of bonding such a compound (QY) to a glass substrate.
As a method for bonding the compound (QY) as exemplified to the functional group Z present on the surface of the glass substrate, the compound (QY) is dissolved or dispersed in an appropriate solvent such as toluene, hexane or acetone. A method of applying the solution or dispersion to the surface of the glass substrate or a method of immersing the glass substrate in the solution or dispersion may be applied. At this time, the concentration of the compound (QY) in the solution or in the dispersion is preferably 0.01% by mass to 30% by mass, and particularly preferably 0.1% by mass to 15% by mass. As a liquid temperature in the case of making it contact, 0 to 100 degreeC is preferable. The contact time is preferably 1 second to 50 hours, and more preferably 10 seconds to 10 hours.

There is no restriction | limiting in particular in the glass substrate used in this invention, All are applicable if it is a glass substrate which has functional groups (Z), such as a hydroxyl group, on the base-material surface.
In general, flat glass substrates used for various conductive materials are used, but they are not necessarily limited to flat glass substrates, and the same applies to glass substrate surfaces of arbitrary shapes such as cylindrical shapes. A graft polymer can be introduced into the.

Examples of the glass substrate suitable for the present invention include a silicon glass substrate, a non-alkali glass substrate, a quartz glass substrate, and a substrate formed by forming an ITO film on the surface of a glass substrate.
The thickness of the glass substrate is selected according to the purpose of use and is not particularly limited, but is generally about 10 μm to 10 cm.

  And after a compound (QY) is couple | bonded with the glass substrate surface in this way, a graft polymer production | generation process is performed.

  In this graft polymer generation step, a radically polymerizable unsaturated compound (for example, a hydrophilic monomer) that is a material of the desired graft polymer is brought into contact with the glass substrate that has been subjected to the above-described photocleavable compound bonding step. After that, energy is applied by exposure or the like, the polymerization initiation group in the exposed region is activated to generate a radical, and a grafting reaction occurs between the radical and an unsaturated compound capable of radical polymerization. Make it progress. As a result, by performing overall exposure, a uniform graft polymer is generated over the entire area of the glass substrate surface.

  As a method of bringing the radically polymerizable unsaturated compound into contact with the glass substrate surface, a method of applying a solution or a dispersed dispersion in which the radically polymerizable unsaturated compound is dissolved, a glass in the solution or the dispersed dispersion There is a method of immersing the substrate.

As the unsaturated compound capable of radical polymerization used in the graft polymer production step, any compound having a radical polymerizable group can be used. For example, hydrophilic monomers, hydrophobic monomers, macromers, oligomers can be used. And polymers having a polymerizable unsaturated group.
In the present invention, from the viewpoint of adhesion and adsorptivity when applying a conductive material, when attaching conductive fine particles, metal ions, etc., a hydrophilic polymer having a hydrophilic group that is a polar group, Hydrophilic macromers and hydrophilic monomers are preferred.
Further, when the conductive film is formed by electroless plating, a compound having a functional group capable of radical polymerization and a functional group that interacts with the electroless plating catalyst or its precursor is used. As such a compound, the same compound as the radically polymerizable unsaturated compound having a polar group described above is used, and the polar group corresponds to the functional group that interacts with the electroless plating catalyst or its precursor. .
Specific examples of the unsaturated compound capable of radical polymerization that are preferably used in the graft polymer production step are shown below.

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

Such a radically polymerizable group-containing hydrophilic polymer can be synthesized as follows.
As a synthesis method, (a) a method of copolymerizing a hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group, (b) copolymerizing a hydrophilic monomer and a monomer having a double bond precursor, Next, a method of introducing a double bond by treatment with a base or the like, and (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group. Among these, from the viewpoint of synthesis suitability, (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group is particularly preferable.

In the methods (a) and (b), the hydrophilic monomer used for the synthesis of the radical polymerizable group-containing hydrophilic polymer includes (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali. Metal salt and amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, 3-vinylpropion Acid or alkali metal salt and amine salt thereof, vinyl sulfonic acid or alkali metal salt and amine salt thereof, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfone Monomers having hydrophilic groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups or salts thereof, hydroxyl groups, amide groups and ether groups, such as acid phosphooxypolyoxyethylene glycol mono (meth) acrylate Can be mentioned.
As the hydrophilic polymer used in the method (c), a hydrophilic homopolymer or copolymer obtained using at least one selected from these hydrophilic monomers is used.

  When the radically polymerizable group-containing hydrophilic polymer is synthesized by the method (a), examples of the monomer having an ethylene addition polymerizable unsaturated group that is copolymerized with the hydrophilic monomer include an allyl group-containing monomer. Examples include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.

  Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (b), a monomer having a double bond precursor that is copolymerized with a hydrophilic monomer is 2- (3-chloro-1-oxopropoxy). ) Ethyl methacrylate.

  Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (c), a reaction between a carboxyl group, an amino group or a salt thereof in the hydrophilic polymer and a functional group such as a hydroxyl group and an epoxy group is performed. It is preferable to introduce an unsaturated group using it. Examples of the monomer having an addition polymerizable unsaturated group used for this purpose include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

-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 monomer-
The hydrophilic monomer may be a monomer having a positive charge such as ammonium or phosphonium, or an acid having a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group or capable of dissociating into a negative charge. Examples thereof include monomers having a group, but other hydrophilic monomers having a nonionic group such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, and a cyano group can also be used.

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, etc. 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.

-Solvent-
The solvent for dissolving and dispersing the above-mentioned radically polymerizable unsaturated compound is not particularly limited as long as the compound and additives added as necessary can be dissolved.
For example, when a hydrophilic compound such as a hydrophilic monomer is applied, an aqueous solvent such as water or a water-soluble solvent is preferable, and a mixture thereof or a solvent in which a surfactant is further added is preferable. . The water-soluble solvent refers to a solvent miscible with water in an arbitrary ratio, and examples of such a water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerin, acids such as acetic acid, Examples thereof include ketone solvents such as acetone, amide solvents such as formamide, and the like.
In addition, when a hydrophobic compound such as a hydrophobic monomer is applied, an alcohol solvent such as methanol, ethanol, 1-methoxy-2-propanol, a ketone solvent such as methyl ethyl ketone, or a hydrocarbon such as toluene. A solvent of the system is preferable.

  There is no particular limitation on the energy application method that can be used in the graft polymer production step, and it may be exposure, heating, or both as long as it can provide energy that causes cleavage at the polymerization initiation site (Y). When implemented, it may be ultraviolet light or visible light. Here, examples of the light source used for the exposure include ultraviolet light, deep ultraviolet light, and visible light, and ultraviolet light and visible light are preferable.

In this way, a graft polymer is generated over the entire surface of the glass substrate. The glass substrate after energy application is subjected to a treatment such as solvent immersion to remove the remaining homopolymer and purify it. Specific purification methods include washing with water or acetone, drying, and the like. From the standpoint of homopolymer removability, it is preferable to employ means such as ultrasonic waves for cleaning.
In the glass substrate after purification, the homopolymer remaining on the surface is completely removed, and only the graft polymer firmly bonded to the glass substrate exists over the entire surface of the glass substrate.

  In the method for forming a conductive glass substrate of the present invention, after forming the graft polymer formation region by the above-described step, (1) a step of attaching conductive fine particles, (2) applying a metal ion or a metal salt, A step of depositing metal by reducing metal ions or metal ions in the metal salt, (3) a step of electroless plating by applying an electroless plating catalyst or a precursor thereof, and (4) a conductive monomer The conductive film is formed by performing any one of the steps of applying and causing a polymerization reaction to form a conductive polymer layer.

(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.
The fine particles having high density and positive charge on the surface are, for example, the method of Toru Yonezawa et al.
T. T. et al. Yonezawa, Chemistry Letters. , 1999
page 1061, T.I. Yonezawa, Languir 2000, vol16, 5218 and Toru Yonezawa, Polymer preprints,
Japan vol. 49.2911 (2000). Yonezawa et al. Show that metal-sulfur bonds can be used to chemically modify the surface of metal particles with a functional group 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. .
Here, when it is going to obtain a transparent wiring board etc., from a viewpoint of ensuring light transmittance, Preferably it is 0.2-100 nm, More preferably, the thing of the range of 1-10 nm is used.

It is preferable from the viewpoint of durability that these fine particles are bonded in the maximum amount capable of being adsorbed to the polar group of the graft polymer. Further, from the viewpoint of ensuring conductivity, the dispersion concentration of the dispersion is preferably about 10 to 20% by weight.
Examples of the method for adsorbing the conductive particles on the polar group include a method in which a liquid in which conductive particles having a charge are dissolved or dispersed on the surface is applied to the glass substrate surface, and the glass in the solution or dispersion. Examples include a method of immersing the substrate. In both cases of application and immersion, the contact time between the solution or dispersion and the support surface is provided because an excessive amount of conductive particles is supplied and introduced by sufficient ionic bonding between the polar groups. Is preferably about 10 seconds to 180 minutes, more preferably about 1 minute to 100 minutes.
The conductive particles are not limited to one type, and a plurality of types can be used in combination as necessary. In order to obtain desired conductivity, a plurality of materials can be mixed and used in advance.

(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 deposit a metal. In the aspect of (2) in the conductive substance applying step according to the present invention. The step of applying a metal ion or metal salt to the graft polymer (metal ion or metal salt applying step), the step of reducing the metal ion or metal ion in the metal salt to precipitate the metal (metal (fine particle) film By performing the 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, by reducing the adsorbed metal ions, etc., a single metal precipitates in the graft polymer region, and depending on the precipitation mode, a metal thin film is formed or a metal fine particle adhesion layer is formed by dispersing metal fine particles. Will be.

In the embodiment (2), the method for imparting a metal ion or metal salt can be appropriately selected depending on the compound forming the graft polymer. The graft polymer preferably has a hydrophilic group from the viewpoint of adhesion of metal ions and the like.
As a specific method for imparting a metal ion or metal salt, (2-1) when the graft polymer has an ionic group (polar group), a method of adsorbing the metal ion to the ionic group of the graft polymer, ( 2-2) A method of impregnating a graft polymer with a metal salt or a solution containing a metal salt when the graft polymer has a high affinity for a metal salt such as polyvinylpyrrolidone, (2-3) hydrophilic graft Either a method of immersing the polymer in a solution containing a metal salt or a solution in which the metal salt is dissolved, and impregnating the graft polymer with a solution containing a metal ion and / or a metal salt is appropriately selected. Can be used. In particular, according to the method (2-3), since the properties of the graft polymer are not particularly limited, a desired metal ion or metal salt can be imparted.

(3) A method of performing electroless plating by applying an electroless plating catalyst or a precursor thereof,
In the aspect (3) of the conductive film forming step in the present invention, the graft polymer has an interactive group that interacts with the electroless plating catalyst or a precursor thereof, and the electroless plating catalyst or the precursor thereof. A conductive film is formed by sequentially performing a step of applying (electroless plating catalyst etc. applying step) and a step of forming a metal thin film by performing electroless plating (electroless plating step).
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. 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, MCn, M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom) and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include 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 metal ion or a metal salt to the graft polymer formation region (2-1) when the graft polymer has an ionic group and a method of adsorbing the metal ion to the ionic group, the above metal is used. The salt is dissolved in an appropriate solvent, and the solution containing the dissociated metal ions is applied to the surface of the glass substrate where the graft polymer is present, or the glass substrate having the graft polymer is immersed in the solution. 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.

  When applying a metal ion or metal salt to the graft polymer, (2-2) If the graft polymer has a high affinity for the metal salt, such as polyvinylpyrrolidone, the above metal salt is made fine particles and directly attached. Alternatively, a dispersion is prepared using a suitable solvent in which the metal salt can be dispersed, and the dispersion is applied to the surface of the glass substrate on which the graft polymer is present, or a glass substrate having the graft polymer in the solution May be immersed. Further, when the graft polymer is made of a hydrophilic compound, the graft polymer has high water retention, so that the graft polymer can be impregnated with the dispersion in which the metal salt is dispersed using the high water retention. From the viewpoint of sufficiently impregnating the dispersion, the metal salt concentration or the metal salt concentration of the dispersion to be contacted is preferably in the range of 1 to 50% by mass, and in the range of 10 to 30% by mass. More preferably. The contact time is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.

  When applying a metal ion or a metal salt to a graft polymer, (2-3) immersing a glass substrate having a hydrophilic graft polymer in a solution containing the metal salt or a solution in which the metal salt is dissolved, When a method of impregnating a region containing the conductive graft polymer with a solution containing metal ions and / or metal salts is used, prepare a dispersion using an appropriate solvent in which the metal salts can be dispersed, or The metal salt is dissolved in an appropriate solvent, and a solution containing the dissociated metal ions is prepared, and the dispersion or solution is applied to the glass substrate surface on which the hydrophilic graft polymer is present, or in the solution. What is necessary is just to immerse the glass substrate which has a hydrophilic graft polymer production | generation area | region. Also in this method, similarly to the above, the hydrophilic graft polymer can be impregnated with the dispersion or solution by utilizing the high water retention property of the hydrophilic graft polymer. From the viewpoint of sufficient impregnation of the dispersion or solution, the metal salt concentration or the metal salt concentration of the dispersion to be contacted is preferably in the range of 1 to 50% by mass, and in the range of 10 to 30% by mass. More preferably. 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, after adding a metal ion or metal salt to the surface of the glass substrate on which the graft polymer is present, the surface is prepared by washing with water to remove excess metal salt or metal ion. Examples thereof include a method of immersing a glass substrate in water such as ion exchange 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 glass 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.

[Relationship between the polarity of the hydrophilic group of the hydrophilic compound binding type and the metal ion or metal salt]
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 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 glass 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 process” and the “electroless plating process” in the aspect (3) of the conductive material application process according to 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 having the charge adjusted in this way can interact with the interactive group (polar group) of the graft polymer. By making it act, a metal colloid (electroless plating catalyst) can be made to adhere to a graft polymer.

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

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

  As a method of applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor to a graft polymer, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is dissolved in an appropriate solvent. Then, a solution containing the dissociated metal ions is prepared, and the solution is applied to the surface of the glass substrate on which the graft polymer is present, or the glass 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 (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.
As the types of metals used in the electroless plating bath, copper, tin, lead, nickel, gold, palladium, and rhodium are known, and among these, copper and gold are particularly preferable from the viewpoint of conductivity.
In addition, there are optimum reducing agents and additives according to the above metals.
For example, a copper electroless plating bath is not particularly limited as long as it can provide copper ions as a copper salt. For example, copper sulfate (CuSO ₄ ), copper chloride (CuCl ₂ ), copper nitrate (Cu (NO ₃ ) ₂ ), copper hydroxide (Cu (OH) ₂ ), copper oxide (CuO), cuprous chloride (CuCl) ) Etc. The amount of copper ions present in the bath is generally from 0.005M to 0.1M, preferably from 0.01M to 0.07M. The reducing agent is not particularly limited as long as it can reduce copper ions to metallic copper, but a polymer such as formaldehyde and derivatives thereof and paraformaldehyde, or derivatives and precursors thereof are preferable. The amount of the reducing agent is 0.05M or more, preferably 0.05M to 0.3M in terms of formaldehyde.

The pH adjuster is not particularly limited as long as it can change the pH, and a compound that raises the pH and a compound that lowers the pH are appropriately selected and used according to the purpose. Specific examples of the pH adjuster include NaOH, KOH, HCl, H ₂ SO ₄ , and HF.
The pH of the electroless plating bath is generally in the range of 12.0 to 13.4 (25 ° C.), preferably 12.4 to 13.0 (25 ° C.). Additives include EDTA, a Rochelle salt, trialkanolamine, and the like, which are copper ion stabilizers, and trialkanolamine is preferred from the viewpoint of adhesion between the glass substrate and the plating film. The addition amount of these stabilizers is 1.2 to 30 times, preferably 1.5 to 20 times that of copper ions. Also, the absolute amount of stabilizer present in the bath is preferably in the range of 0.006 to 2.4M, particularly 0.012 to 1.6M.

Examples of the trialkanolamine used as a stabilizer include trimethanolamine, triethanolamine, triisopropanolamine, and tripropanolamine. Triethanolamine is particularly preferable from the viewpoint of adhesion between the glass substrate and the plating film. .
Examples of additives for stabilizing the bath and improving the smoothness of the plating film include polyethylene glycol, potassium ferrocyanide, and bipyridine. The concentration of these additives present in the bath is preferably in the range of 0.001 to 1M, especially 0.01 to 0.3M.

The plating bath used for electroless plating of CoNiP contains cobalt sulfate and nickel sulfate as its metal salt, sodium hypophosphite as the reducing agent, sodium malonate, sodium malate and sodium succinate as the complexing agent. It is. 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, it is preferably 0.5 μm or more, and more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

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

<Electroplating process>
In the aspect (3) of the electroconductive substance provision process which concerns on this invention, after performing the said electroless-plating process, you may have the process (electroplating process) of performing electroplating.
This step is a step of performing electroplating after the electroless plating in the electroless plating step, using the metal film (conductive film) formed in the 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 glass substrate (formed by electroless plating) as a base. 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 a method of electroplating in this step, 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. Note that the film thickness when used for general electrical wiring is preferably 0.3 μm or more, and more preferably 3 μm or more, from the viewpoint of conductivity.

  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 interactive group of the graft polymer, particularly preferably to the ionic group, and is then used as it is. 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 generated 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 glass 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 conductive glass substrate of the present invention thus obtained, a conductive film having excellent adhesion and conductivity is formed on the glass substrate, and its application range is wide. In addition, as described above, a conductive glass substrate having excellent characteristics can be easily manufactured.

[Conductive pattern forming method]
Next, the conductive pattern forming method will be described.
The conductive pattern forming method of the present invention includes a first aspect in which a graft polymer imparting a conductive material is formed in a pattern and a patterned metal film is formed accordingly, and the graft polymer is applied to the entire surface of the substrate. There is a second mode in which after a metal film is formed over the entire surface and a metal film is formed on the entire surface, an etching process is performed to form a patterned metal film.
First, the 1st aspect in the conductive pattern formation method of this invention is demonstrated.
In the first aspect, first, a compound having a polymerization initiation site (Y) capable of initiating radical polymerization by photocleavage and a base material binding site (Q) is bonded to a glass substrate, and radical polymerization is performed on the glass substrate. A pattern exposure is performed by contacting a possible unsaturated compound. By this pattern exposure, in the exposed region, a graft polymer is generated starting from the polymerization initiation site (Y) of the compound (QY) (graft polymer generating region), while in the unexposed region, the graft polymer is Not formed (non-grafted polymer region).
The pattern exposure method in this step is not particularly limited. For example, only a desired region is exposed using a method of performing full-surface exposure through a predetermined mask pattern or laser scanning exposure based on digital data. Can take the way. By this pattern exposure, a high-resolution graft polymer production region can be easily obtained on the glass substrate.

There are no particular limitations on the exposure method that can be used in the graft polymer production step, and ultraviolet light or visible light may be used as long as it can provide energy that causes cleavage at the polymerization initiation site (Y). Further, a light source having a wavelength distribution may be used for exposure, or a light source having a specific wavelength may be used.
Examples of the light source include scanning exposure using a cathode ray (CRT). As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, one or more of a red light emitter, a green light emitter, and a blue light emitter are mixed and used. The spectral region is not limited to the above red, green, and blue, and phosphors that emit light in the yellow, orange, purple, or infrared region are also used. An ultraviolet lamp is also preferable, and i-line of a mercury lamp is also used.

In this step, pattern exposure can be performed using various laser beams. For example, as pattern exposure, a laser such as a gas laser, a light emitting diode, or a semiconductor laser, a second harmonic emission light source (SHG) that combines a solid state laser using a semiconductor laser or a semiconductor laser as an excitation light source and a nonlinear optical crystal, etc. A scanning exposure method using monochromatic high-density light can be preferably used. Further, a KrF excimer laser, an ArF excimer laser, an F2 laser, or the like can also be used.
Furthermore, when performing high-resolution pattern exposure, stepper exposure such as an i-line stepper, KrF stepper, and ArF stepper can be used.

  The pattern exposure may be performed by a method of performing overall exposure using a mask pattern such as a photomask, or may be performed by scanning exposure using a laser beam as described above. The light irradiation method at this time is arbitrary. For example, a refraction exposure using a lens or a reflection exposure using a reflecting mirror may be used, and an exposure method such as contact exposure, proximity exposure, reduction projection exposure, reflection projection exposure, etc. Can be used.

In this way, the substrate on which the pattern composed of the graft polymer generation region and the non-generation region is formed on the substrate surface is subjected to a treatment such as solvent immersion after the exposure to remove the remaining homopolymer and purified. To do. Specifically, washing with water or acetone, drying, and the like can be given. From the viewpoint of homopolymer removability, it is preferable to adopt means such as ultrasonic waves.
The purified base material has the homopolymer remaining on the surface completely removed, and only the patterned graft polymer firmly bonded to the base material is present.
The graft polymer pattern composed of the graft polymer generation region and the non-generation region obtained in the above process becomes a fine pattern according to the exposure resolution.

  Next, a conductive material is applied to the graft polymer generation region to form a conductive film. As described above, the conductive material is applied as follows: (1) a method of attaching conductive fine particles, (2) applying a metal ion or metal salt, and then reducing the metal ion or metal ion in the metal salt. A method of depositing a metal, (3) a method of applying an electroless plating catalyst or a precursor thereof to perform electroless plating, and (4) a conductive polymer layer by applying a conductive monomer and causing a polymerization reaction. It is a preferable aspect that it is made by any method selected from the method of forming.

Next, the 2nd aspect of the conductive pattern formation method of this invention is demonstrated.
The second aspect of the conductive pattern forming method of the present invention is a method for forming a conductive pattern by etching the conductive glass substrate of the present invention, that is, a metal film formed over the entire surface of the glass substrate. is there. Hereinafter, the conductive pattern forming method will be described in the order of steps.

[Etching process]
By performing an etching process on the conductive film (metal film) formed on the glass substrate, a metal pattern having excellent adhesion to the glass substrate can be formed. “Subtractive method” and “semi-additive method” are used as an etching method in forming a metal pattern by etching the conductive film obtained by the present invention.

"Subtractive method"
The subtractive method is unnecessary by (1) applying a resist layer on the conductive film created by the above method → (2) forming a resist pattern of a conductor to be left by pattern exposure and development → (3) etching. Remove conductive film → (4) A method of peeling a resist layer and forming a metal pattern. The thickness of the conductive 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, it can form a pattern with good resolution, has good follow-up to unevenness on the coated surface, and has excellent adhesion. 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 substrate in which a resist film is provided on the conductive 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-curing negative resist can be used as long as it can dissolve the unexposed area, or a photo-dissolving positive resist that dissolves upon exposure, so long as it can dissolve 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 uneven, the conductive polymer in the vicinity of the substrate interface has good removability, and the graft polymer in which the conductive film is introduced onto the glass substrate is a polymer chain. In this etching process, the etching solution can be easily diffused into the graft polymer layer and the interface between the glass 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 as follows: (1) Apply a resist layer on the conductive film formed on the graft polymer → (2) Form a resist pattern of the conductor to be removed by pattern exposure and development → (3) Resist path by plating The conductive pattern is formed on the non-patterned portion of the metal pattern → (4) The DFR is peeled off → (5) An unnecessary conductive film is removed by etching to form a metal pattern. 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 conductive film used is preferably about 1 to 3 μm because the etching process can be completed in a short time. Moreover, you may perform electrolytic plating and electroless plating further with respect to the formed metal pattern.

  The conductive pattern material obtained by the conductive pattern forming method of the present invention has a high-definition and durable high-density metal (fine particle) pattern on a glass substrate surface by a simple process. . Such a conductive pattern material obtained by the conductive pattern forming method of the present invention includes a liquid crystal display element, an organic EL, a display electrode material such as a display element, a printed wiring such as COG (chip on glass), Various applications such as high-density magnetic disks, magnetic heads, magnetic tapes, magnetic sheets, and magnetic disks can be expected, and the application range is wide. Further, it can be used for various circuit formation applications, and a wide range of applications including circuit formation such as micromachines and VLSIs is expected.

  In the present invention, since a transparent glass substrate is used as a base material, it can be used as a patterned transparent conductive substrate. Examples of the use of such a transparent conductive substrate include a transparent electrode for display, a light control device, a solar cell, a touch panel, and other transparent conductive films, but are particularly useful as an electromagnetic wave shielding filter attached to a CRT or a plasma display. . Since such an electromagnetic wave shielding filter requires high conductivity and transparency, it is preferable to provide a metal (fine particle) film in a lattice shape. Such a lattice line width is preferably about 20 to 100 μm, and the opening is preferably about 50 to 600 μm. This lattice does not necessarily have to be regular and configured with straight lines, and may be configured with curved lines.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Synthesis Example 1: Synthesis of Compound A)
The exemplary compound 1 is synthesized by the following two steps. A description will be given of the scheme of each step.
1. Step 1 (Synthesis of Compound a)
24.5 g (0.12 mol) of 1-hydroxycyclohexyl phenyl ketone was dissolved in a mixed solvent of 50 g of DMAc and 50 g of THF, and 7.2 g (0.18 mol) of NaH (60% in oil) was gradually added in an ice bath. Thereto, 44.2 g (0.18 mol) of 11-bromo-1-undecene (95%) was added dropwise and reacted at room temperature. The reaction was completed in 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate to obtain a mixture containing Compound a in the form of a yellow solution. 37 g of this mixture was dissolved in 370 ml of acetonitrile, and 7.4 g of water was added. 1.85 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 20 minutes. The organic phase was extracted with ethyl acetate and the solvent was distilled off. Compound a was isolated by column chromatography (filler: Wakogel C-200, developing solvent: ethyl acetate / hexane = 1/80).
A synthesis scheme is shown below.

1H NMR (300 MHz CDCl ₃ )
δ = 1.2-1.8 (mb, 24H), 2.0 (q, 2H), 3.2 (t, J = 6.6, 2H), 4.9-5.0 (m, 2H) ) 5.8 (ddt, J = 24.4, J = 10.5, J = 6.6, 1H.), 7.4 (t, J = 7.4, 2H), 7.5 (t, J = 7.4, 1H), 8.3 (d, 1H)

2. Step 2 (Synthesis of Compound A by Hydrosilylation of Compound a)
Two drops of Spear catalyst (H ₂ PtCl ₆ .6H ₂ O / 2-PrOH, 0.1 mol / l) was added to 5.0 g (0.014 mol) of compound a, and 2.8 g (0.021 mol) of trichlorosilane in an ice bath. ) Was added dropwise and stirred. After 1 hour, 1.6 g (0.012 mol) of trichlorosilane was added dropwise, and the temperature was returned to room temperature. The reaction was complete after 3 hours. After completion of the reaction, unreacted trichlorosilane was distilled off under reduced pressure to obtain Compound A.
A synthesis scheme is shown below.

1H NMR (300 MHz CDCl ₃ )
δ = 1.2−1.8 (m, 30H), 3.2 (t, J = 6.3, 2H), 7.3-7.7 (m, 3H), 8.3 (d, 2H) )

(Synthesis Example 2: Synthesis of hydrophilic polymer P having a polymerizable group)
18 g of polyacrylic acid (average molecular weight 25,000) is dissolved in 300 g of DMAc (dimethylacetamide), and 0.41 g of hydroquinone, 19.4 g of 2-methacryloyloxyethyl isocyanate and 0.25 g of dibutyltin dilaurate are added thereto. The reaction was carried out at 65 ° C. for 4 hours. The acid value of the obtained polymer was 7.02 meq / g. The carboxyl group was neutralized with a 1 mol / l sodium hydroxide aqueous solution, the polymer was precipitated in addition to ethyl acetate, and washed well to obtain a hydrophilic polymer P having a polymerizable group.

[Example 1]
(Photocleavable compound binding step)
A glass substrate (Japanese plate glass) was immersed in a piranha solution (sulfuric acid / 30% hydrogen peroxide = 1/1 vol mixed solution) overnight, and then washed with pure water. The substrate was placed in a separable flask purged with nitrogen and immersed in a 12.5 wt% dehydrated toluene solution of Compound A for 1 hour. After taking out, it wash | cleaned in order with toluene, acetone, and a pure water. Let the obtained base plate be the board | substrate A1.

(Graft polymer production process)
Hydrophilic polymer P (0.5 g) was dissolved in a mixed solvent of 4.0 g of pure water and 2.0 g of acetonitrile to prepare a coating solution for a graft forming layer. The graft forming layer coating solution was applied to the substrate A1 with a spin coater. The spin coater was first rotated at 300 rpm for 5 seconds and then at 1000 rpm for 20 seconds. The substrate A1 after application of the graft forming layer was dried at 100 ° C. for 2 minutes. The thickness of the graft-forming layer after drying was 2 μm.

(exposure)
The surface of the glass substrate coated with the graft forming layer was exposed for 1 minute with an exposure machine (UVX-02516S1LP01, manufactured by USHIO INC.). After the exposure, it was thoroughly washed with pure water.
As described above, a conductive glass substrate A was formed.
The obtained substrate A was observed with AFM (Nanopics 1000, manufactured by Seiko Instruments Inc., using a DFM cantilever). As a result, it was confirmed that a graft polymer layer was formed on the surface.

(Electroless plating)
The obtained substrate A was immersed in an aqueous solution of 0.1% by mass of palladium nitrate (manufactured by Wako Pure Chemical Industries) for 1 hour, and then washed with distilled water. Thereafter, electroless plating was performed in an electroless plating bath having the following composition for 20 minutes to produce a conductive glass substrate 1 having a metal film (conductive film 1) on the surface.

<Composition of electroless plating bath>
・ 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

[Example 2]
The metal film formed in Example 1 was further electroplated for 15 minutes to produce a conductive glass substrate 2 having a metal film (conductive film 2) on the surface.

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

Example 3
(Photocleavable compound binding step)
A glass substrate (Nippon Sheet Glass Co., Ltd.) was subjected to UV ozone treatment for 5 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.). The surface of the substrate was spin-coated with Compound A (obtained in Synthesis Example 1) dissolved in dehydrated toluene to make a 1.0% solution. The spin coater was first rotated at 300 rpm for 5 seconds and then at 1000 rpm for 20 seconds. The glass substrate on which the compound A was spin-coated was dried at 100 ° C. for 2 minutes, and the surface was washed with toluene, acetone and water in that order and dried with an air gun. The obtained substrate is designated as A2.

(Graft polymer production process)
Hydrophilic polymer P (0.25 g) was dissolved in a mixed solvent of 1.91 g of water, 0.09 g of DMAc and 1 g of acetonitrile to obtain a coating solution for a graft forming layer. The graft forming layer coating solution was spin coated on the surface of the A2 substrate. The spin coater was first rotated at 300 rpm for 5 seconds and then at 1000 rpm for 20 seconds. The substrate A2 after application for the graft forming layer was dried at 80 ° C. for 5 minutes.
(exposure)
The substrate A2 after application for the graft forming layer was exposed for 5 minutes with an exposure machine (UVX-02516S1LP01, manufactured by USHIO INC.). After the exposure, the substrate surface was washed with water while being lightly rubbed with a wiper (Bencott, manufactured by Ozu Sangyo Co., Ltd.).
As described above, a glass substrate B on which the graft polymer was formed over the entire surface was formed.

(Electroless plating)
The obtained substrate B was immersed in a 0.1% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 5 minutes, washed with water, and dried with an air gun. Thereafter, electroless plating was performed by immersing in an electroless plating bath (pH: 12.7) having the following composition for 20 minutes. After electroless plating, it was washed with water and dried with an air gun.

<Composition of electroless plating bath>
300 g of water
Copper (II) sulfate pentahydrate 4.5g
8.04 g of triethanolamine
Polyethylene glycol (average molecular weight 1000) 0.03g
Sodium hydroxide 2.7g
Formaldehyde solution (36.0-38.0%) 5.4g

(Electroplating)
The electroless-plated substrate using the electroless plating bath was further electroplated for 20 minutes to produce a conductive glass substrate 3 having a metal film (conductive film 3) on the surface. The composition of the electroplating bath is the same as that of the electroplating bath used in Example 2.

Example 4
The glass substrate B with the graft polymer formed on the surface produced in Example 3 was immersed in a 0.1% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 5 minutes, washed with water and dried with an air gun. Thereafter, electroless plating was performed by dipping for 20 minutes in an electroless plating bath (pH: 12.4) having the following composition. After electroless plating, it was washed with water and dried with an air gun.

<Composition of electroless plating bath>
200g of water
Copper (II) sulfate pentahydrate 2.9g
(+)-Potassium sodium tartrate tetrahydrate 21.3 g
Sodium hydroxide 1.65g
Formaldehyde solution (36.0-38.0%) 5.5ml
Add water to make the whole 250ml

(Electroplating)
The electroless-plated substrate using the electroless plating bath was further electroplated for 20 minutes to produce a conductive glass substrate 4 having a metal film (conductive film 4) on the surface. The composition of the electroplating bath is the same as that of the electroplating bath used in Example 2.

Example 5
The initiator-bonded glass substrate prepared in Example 1 was immersed in an aqueous solution containing acrylic acid (10 wt%) and sodium periodate (NaIO ₄ , 0.01 wt%), and the above 1.5 kW under an argon atmosphere. Was irradiated with light for 10 minutes. After light irradiation, the substrate was thoroughly washed with ion-exchanged water, and a surface graft polymer of acrylic acid was introduced to the entire substrate to obtain a graft substrate C.
(Adhesion of conductive material)
Conductive material prepared by the following method: Immersing the graft substrate C prepared above in a positively charged Ag fine particle dispersion, and then thoroughly washing the surface with running water to remove excess Ag dispersion, A conductive glass substrate 5 having a conductive film 5 made of conductive Ag fine particles was produced.

<Method for producing conductive material>
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. When the size of the silver particles (Ag particles) was measured with an electron microscope, the average particle size was 5 nm.

Example 6
The conductive film 5 obtained in Example 5 was heated at 300 ° C. for 1 hour to produce a conductive glass substrate 6 having a conductive conductive film 6 on the surface.

Example 7
(Photocleavable compound binding step)
Using an ITO-deposited glass substrate (Nippon Sheet Glass Co., Ltd., surface resistance 10Ω / □, product number. 49J183), ultrasonically wash in order of isopropyl alcohol, acetone, methanol, and pure water for 5 minutes or more, respectively. Spray dried. The substrate was placed in a separable flask purged with nitrogen and immersed in a dehydrated toluene solution of 12.5 wt% of Compound A for 1 hour to overnight. After taking out, it wash | cleaned in order with toluene, acetone, and a pure water.
(Graft polymer production process)
In the same manner as in Example 1, a graft polymer production coating solution was applied to the substrate and dried. The thickness of the graft polymer production layer after drying was 2 μm. Next, overall exposure was performed in the same manner as in Example 1. After the exposure, it was thoroughly washed with pure water. A graft substrate D formed on ITO was obtained.
Next, graft substrate D was prepared from sodium anthraquinone-2-sulfonate 1.23 g, sodium 5-sulfosalicylic acid 7.20 g, and iron trichloride hexahydrate. It was immersed in a solution consisting of 4.38 g and 125 ml of water, and a solution of 0.75 ml of pyrrole and 125 ml of water was added with stirring. One hour later, the substrate was taken out, washed with water, and then washed with acetone to obtain a conductive glass substrate 7 having a polypyrrole layer (conductive polymer layer) formed on the surface of the ITO substrate.

<Evaluation of conductivity>
For the conductive glass substrates 1 to 7 obtained as described above, the surface conductivity of the portion where the conductive film was formed was measured by a four-probe method using a Loresta-FP (LORESTA-FP: manufactured by Mitsubishi Chemical Corporation). did. The results are shown in Table 1 below.

<Evaluation of conductive film adhesion>
About the electrically conductive film of the conductive glass substrates 1-7, film | membrane adhesiveness was evaluated by the cross-cut tape method according to JIS5400. A tape peeling test was performed on the cut grids. The number of grids remaining on the substrate side among the 100 grids is shown in Table 1 below.

  As is apparent from Table 1, it can be seen that all of the conductive glass substrates of the present invention have excellent conductivity and adhesion.

Example 8
A pattern mask (NC-1, manufactured by Toppan Printing Co., Ltd.) is clipped onto the substrate A2 coated with the layer made of the compound A for forming the graft polymer prepared in Example 3 and exposed to light (UVX- 02516S1LP01, manufactured by USHIO INC. For 1 minute. After exposure, the mask was removed and washed thoroughly with pure water.
As described above, a graft pattern substrate A1 having a graft polymer generation region and a non-generation region was formed.
The obtained graft pattern substrate A1 was observed with AFM (Nanopics 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a graft polymer pattern having a line width of 8 μm and a gap width of 8 μm alternately formed on the substrate surface was formed.

(Formation of metal (fine particle) film)
The graft pattern substrate A1 was immersed in a 15% by mass aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 12 hours and then washed with distilled water. Thereafter, the adsorbed silver ions were reduced by immersing the substrate in 100 ml of distilled water and dropping 30 ml of 0.2 mol / l sodium tetrahydroborate into the distilled water. As a result, the graft pattern substrate A1 was reduced. On the surface, a uniform Ag metal film (metal (fine particle) film) was formed only in the graft polymer formation region. The formed Ag metal film had a thickness of 0.1 μm. As a result, a conductive pattern material A1 in which an Ag (fine particle) film was formed in a pattern was obtained.
When this surface was observed with an electron microscope, it was found that a good conductive pattern in which a line width of 8 μm and a gap width of 8 μm exist alternately was formed.

Example 9
The graft pattern substrate A1 obtained in the same manner as in Example 8 was immersed in a 0.1% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 5 minutes, washed with water, and dried with an air gun. Thereafter, electroless plating was performed by immersing in an electroless plating bath (pH: 12.7) having the following composition for 20 minutes. After electroless plating, it was washed with water and dried with an air gun to produce a conductive pattern material A2.
When this surface was observed with an electron microscope, it was found that a good conductive pattern in which a line width of 8 μm and a gap width of 8 μm exist alternately was formed.

<Composition of electroless plating bath>
300 g of water
Copper (II) sulfate pentahydrate 4.5g
8.04 g of triethanolamine
6.7mg potassium ferrocyanide
2,2'-bipyridyl 3.5mg
Sodium hydroxide 2.7g
Formaldehyde solution (36.0-38.0%) 5.4g

Example 10
The graft pattern substrate A1 obtained in the same manner as in Example 8 was immersed in a conductive material: positive charge Ag fine particle dispersion prepared by the following method, and then the surface was sufficiently washed with running water to remove excess Ag. The dispersion was removed, and a pattern material composed of conductive Ag fine particles on the surface was produced. Then, electroconductive pattern material A3 was produced by heating at 300 degreeC for 1 hour.

<Method for producing conductive material>
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. When the size of the silver particles (Ag particles) was measured with an electron microscope, the average particle size was 5 nm.

Example 11
Graft pattern substrate A1 obtained in the same manner as in Example 8, 1.23 g of sodium anthraquinone-2-sulfonate · monohydrate, 7.20 g of sodium 5-sulfosalicylic acid · hydrate, and It was immersed in a solution consisting of 4.38 g of iron trichloride hexahydrate and 125 ml of water, and a solution of 0.75 ml of pyrrole and 125 ml of water was added with stirring. One hour later, the substrate was taken out, washed with water, and then washed with acetone, thereby producing a conductive pattern material A4 having a polypyrrole layer (conductive polymer layer) formed on the surface.

Example 12
On the substrate A2 coated with the layer made of the compound A for forming the graft polymer prepared in Example 3, the pattern was exposed directly with a 355 nm laser. After the exposure, it was thoroughly washed with pure water.
As described above, a graft pattern substrate B1 having a graft polymer generation region and a non-generation region on the substrate surface was produced.
The surface of the obtained graft pattern substrate B1 was observed with AFM (Nanopics 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a graft polymer pattern having a line width of 20 μm and a gap width of 20 μm alternately formed.

The graft pattern substrate B1 was immersed in a 0.1% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 5 minutes, washed with water, and dried with an air gun. Thereafter, electroless plating was performed by immersing in an electroless plating bath (pH: 12.6) having the following composition for 20 minutes. After electroless plating, it was washed with water and dried with an air gun to produce a conductive pattern material B.
When this surface was observed with an electron microscope, it was found that a good conductive pattern having alternating line widths of 20 μm and void widths of 20 μm was formed.

<Composition of electroless plating bath>
300 g of water
Copper (II) sulfate pentahydrate 4.6g
Triethanolamine 8.05g
Potassium ferrocyanide 6.6mg
2,2′-bipyridyl 3.4 mg
Sodium hydroxide 2.7g
Formaldehyde solution (36.0-38.0%) 5.6g

Example 13
A photosensitive dry film (VANX HL-020: manufactured by Fuji Photo Film) is laminated on the conductive film surface of the conductive glass substrate on which the metal film 2 obtained in Example 2 is formed, and a desired conductor circuit pattern is drawn. The film was exposed to ultraviolet light through a mask film (the metal pattern portion was an opening, and the metal pattern non-formed portion was a mask portion), and the image was printed and developed. Next, the metal film (copper thin film) where the resist was removed was removed using a cupric chloride etching solution. Thereafter, the dry film was peeled off to obtain a conductive pattern material C having a line width of 25 μm (measured using an optical microscope, trade name: OPTI PHOTO-2, manufactured by Nikon Corporation).

(Evaluation of conductivity)
Regarding the conductive pattern materials A1, A2, A3, A4, B, and C obtained in Examples 8 to 13, the surface conductivity of the portion where the conductive pattern was formed was determined to be LORESTA-FP (Mitsubishi Chemical Corporation )) And the four-probe method. The results are shown in Table 2 below.

(Evaluation of film strength (adhesion))
The conductive pattern materials A1, A2, A3, A4, B, and C were subjected to a tape peeling test directly on the metal pattern formed without the grid cut in accordance with JIS 5400 grid tape method. However, no peeling was observed, and it was confirmed that the adhesion between the substrate and the metal thin film was good.

(Durability evaluation)
The surfaces of the conductive pattern materials A1, A2, A3, A4, B, and C were rubbed 30 times by hand using a cloth (BEMCOT, manufactured by Asahi Kasei Kogyo Co., Ltd.) wetted with water. When the surface was visually observed after rubbing, no peeling of the metal (fine particle) film was observed for the conductive pattern materials A1, A2, A3, A4, B, and C.
In addition, when the sample after rubbing was subjected to a tape peeling test in the same manner as described above, the conductive pattern materials A1, A2, A3, A4, B, and C were not peeled off at all. In addition, it was confirmed that the adhesion between the metal (fine particle) film and the substrate did not deteriorate and was excellent in durability.

  As described above, the conductive pattern material obtained by using the conductive pattern forming method of the present invention is formed with a high-definition conductive pattern having sufficient conductivity, and the adhesion between the substrate and the metal film. And it was found to be excellent in durability.

Claims (19)

  A conductive glass substrate, wherein a conductive material is imparted to a graft polymer directly chemically bonded to a glass substrate.   An unsaturated compound capable of radical polymerization is brought into contact with a glass substrate formed by bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a base material binding site to the surface, and energy is applied thereto. A conductive glass substrate obtained by forming a graft polymer on a glass substrate and then applying a conductive material to the graft polymer generation region.   Application of the conductive material includes (1) a method of attaching conductive fine particles, (2) metal ions or metal salts, and then reducing the metal ions or metal ions in the metal salts to reduce the metal. (3) A method of performing electroless plating by applying an electroless plating catalyst or a precursor thereof, (4) A method of forming a conductive polymer layer by applying a conductive monomer and causing a polymerization reaction The conductive glass substrate according to claim 2, wherein the conductive glass substrate is made by any method selected from.   The method of (3) applying an electroless plating catalyst or a precursor thereof and performing electroless plating, wherein the electroless plating is performed using an electroless plating bath containing a trialkanolamine. 3. The conductive glass substrate according to 3.   The conductive glass substrate according to claim 4, wherein the trialkanolamine is triethanolamine. Binding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a substrate binding site to a glass substrate;
An unsaturated compound capable of radical polymerization is brought into contact with the glass substrate, energy is applied, and radicals are generated from the compound having a polymerization initiation site and a base material binding site capable of initiating radical polymerization by the photocleavage, Producing a graft polymer formed by bonding it to a glass substrate using it as a starting species;
Providing a conductive material to the generated graft polymer to form a conductive film;
A method for forming a conductive glass substrate, comprising:   The step of forming a conductive film by applying a conductive substance to the generated graft polymer includes (1) a step of attaching conductive fine particles to the generated graft polymer, and (2) a metal ion or a metal salt on the generated graft polymer. And then depositing metal by reducing the metal ions or metal ions in the metal salt, and (3) applying an electroless plating catalyst or a precursor thereof to the resulting graft polymer, and electroless plating 7. The method according to claim 6, wherein the step is selected from: a step of performing a step (a), and (4) a step of imparting a conductive monomer and then causing a polymerization reaction to form a conductive polymer layer. A method for forming a conductive glass substrate.   (3) In the step of imparting an electroless plating catalyst or a precursor thereof to the generated graft polymer and performing electroless plating, electroless plating is performed using an electroless plating bath containing trialkanolamine. The method for forming a conductive glass substrate according to claim 7, wherein:   The method for forming a conductive glass substrate according to claim 8, wherein the trialkanolamine is triethanolamine.   The polymerization initiation site includes any one selected from the group consisting of C—C bond, C—N bond, C—O bond, C—Cl bond, N—O bond, and S—N bond. The method for forming a conductive glass substrate according to any one of claims 6 to 9. Binding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a substrate binding site to a glass substrate;
A step of bringing a unsaturated compound capable of radical polymerization into contact with a glass substrate and exposing it in a pattern to form a graft polymer generation region and a non-generation region;
Providing a conductive material to the graft polymer formation region to form a conductive film;
And a surface resistance value of the obtained conductive film is 0.1 to 20Ω / □.   The method for forming a conductive pattern according to claim 11, wherein a glass substrate treated with UV ozone is used as the glass substrate.   The step of forming a conductive film by applying a conductive substance to the generated graft polymer includes (1) a step of attaching conductive fine particles to the generated graft polymer, and (2) a metal ion or a metal salt on the generated graft polymer. And then depositing metal by reducing the metal ions or metal ions in the metal salt, and (3) applying an electroless plating catalyst or a precursor thereof to the resulting graft polymer, and electroless plating Or (4) applying a conductive monomer, and then causing a polymerization reaction to form a conductive polymer layer. Item 13. The conductive pattern forming method according to Item 12.   (3) In the step of imparting an electroless plating catalyst or a precursor thereof to the generated graft polymer and performing electroless plating, electroless plating is performed using an electroless plating bath containing trialkanolamine. The conductive pattern forming method according to claim 13, wherein the conductive pattern is formed.   The conductive pattern forming method according to claim 14, wherein the trialkanolamine is triethanolamine.   The conductive pattern forming method according to claim 11, wherein the pattern exposure method is pattern exposure using a mask pattern.   The method for forming a conductive pattern according to claim 11, wherein the pattern exposure method is pattern exposure by laser scanning exposure.   The conductive pattern formation method which has the process of etching the electrically conductive film of the conductive glass substrate surface of any one of Claims 1 thru | or 5.   The polymerization initiation site includes any one selected from the group consisting of C—C bond, C—N bond, C—O bond, C—Cl bond, N—O bond, and S—N bond. The method for forming a conductive pattern according to any one of claims 11 to 17.