JP2006077273A - Conductive pattern material, its manufacturing method, and pdp - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive pattern material having excellent adhesiveness of an ITO film to a metal film and straightness, and applicable to a lamination type electrode or wire capable of realizing higher precision, and its manufacturing method, and to provide a PDP (plasma display panel) having the conductive pattern material to constitute a lamination type electrode without any disconnection or short circuit as a compound electrode and capable of realizing higher precision. <P>SOLUTION: In the conductive pattern material, graft polymer is directly coupled with a surface of an ITO film provided on a substrate in a pattern shape to deposit the conductive material on the graft polymer. The conductive pattern material manufacturing method comprises a step of providing the ITO film on the substrate, a step of directly coupling graft polymer on the surface of the ITO film, and a step of depositing the conductive material on the graft polymer, and further comprises a step of patterning the ITO film before or after the step of directly coupling the graft polymer. The conductive pattern material obtained by the manufacturing method is applied to the PDP. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a conductive pattern material, a method for producing a conductive pattern material, and a PDP using the conductive pattern material, which are suitable for laminated wiring and electrodes made of an ITO film and a metal film.

2. Description of the Related Art In recent years, flat display devices are used in various fields as display devices for personal computers, word processors, TVs, and the like, and as projection display devices, taking advantage of the characteristics of thinness, light weight, and low power consumption.
In these flat display devices, an ITO film is provided in a desired region on the substrate, and a film is further formed on the ITO film with a metal such as gold, platinum, or copper in order to reduce the resistance value. In many cases, stacked electrodes and wirings formed by stacking these metal films are used.

For example, in a plasma display panel (hereinafter referred to as “PDP”) which is one of flat display devices, a composite electrode provided on a front glass substrate is an example. The composite electrode in the PDP has a high resistance value only with a transparent ITO electrode and cannot be used as an electrode. Therefore, in order to reduce the resistance value, a bus electrode which is a metal electrode is formed on the transparent ITO electrode.
Further, in a liquid crystal display element which is one of flat display devices, when a driving IC chip is mounted on a substrate by a COG method, a metal film is formed on the ITO wiring as an input / output wiring of the driving IC chip. The formed one is used. The input / output wiring of this driving IC chip is formed by forming a metal coating on the ITO wiring formed in a desired pattern in order to reduce the resistance value.

These electrodes and wirings are first formed of ITO by sputtering, ion plating, vacuum deposition, CVD, or the like. Then, this thin film is patterned into a desired pattern using a photolithography process to form an ITO film having a desired pattern, and then a metal film is formed. As a material for the metal film, Ag, Au, Ni, Al, Pt, Cu, and alloys thereof having good conductivity and excellent corrosivity, and metal pastes containing these are used. These metal materials are formed or coated on the patterned ITO film. Examples of film forming methods include sputtering, ion plating, vacuum deposition, and CVD. Examples of coating methods include screen printing, blade coating, die coating, and coating with a dispenser. Then, after apply | coating a metal paste, a baking process is performed. Thereafter, by patterning the metal material into a desired pattern, a stacked electrode or wiring of the ITO film and the metal film can be obtained.
In addition, after laminating | stacking an ITO film | membrane and a metal film, a laminated electrode and wiring can be obtained also by patterning in order of a metal film and an ITO film | membrane.

However, such a laminate of an ITO film and a metal film has a drawback of poor interface adhesion. When the adhesion between the ITO film and the metal film is low, problems such as fear of disconnection and insufficient electrical conductivity occur. Therefore, generally, a method has been employed in which a chromium vapor deposition film is formed in advance on the ITO film, and a metal film is further formed on the chromium vapor deposition film. According to this method, a certain degree of adhesion is imparted between the ITO film and the metal film, but since a chromium vapor deposition step is required, there is a problem that the cost increases. Therefore, the present situation is that a stacked electrode or wiring having excellent adhesion between the ITO film and the metal film is desired without requiring a chromium vapor deposition step.
In addition, when a metal paste is used when forming a metal film, a firing step is required. However, if the particle size of the metal particles in the metal paste is large, the electrodes and wiring obtained through this firing step are linear. Also had the problem of being extremely bad.

  On the other hand, there is an increasing demand for miniaturization, high definition, and high density for flat display devices including these stacked electrodes and wirings. Accordingly, conductors used in such flat display devices are increasing. There is a demand for improvement in miniaturization (high definition) technology of wiring patterns in circuits. Therefore, miniaturization and high resolution are also desired for stacked electrodes and wirings of ITO film and metal film, but when the metal film is patterned as described above, the metal film remains, Due to the residual metal film, there is a problem that a short circuit between the wirings occurs.

An object of the present invention is to solve various problems in the prior art and achieve the following objects.
That is, the first object of the present invention is to provide a conductive pattern material that can be applied to stacked electrodes and wiring that are excellent in adhesion and linearity between the ITO film and the metal film, and that can be further refined. And a manufacturing method thereof.
A second object of the present invention is to provide a PDP that is provided with a conductive pattern material constituting a laminated electrode without disconnection or short-circuiting as a composite electrode, and can achieve high definition.

  The present invention has been made in view of the above-mentioned drawbacks of the prior art, and an object thereof is to achieve the following object.

That is, the conductive pattern material of the present invention is characterized in that the graft polymer is directly bonded to the ITO film surface provided in a pattern on the substrate, and the conductive material is attached to the graft polymer. .
The method for producing a conductive pattern material of the present invention includes a step of providing an ITO film on a substrate, a step of directly bonding a graft polymer to the surface of the ITO film, and a step of attaching a conductive material to the graft polymer. And having a step of patterning the ITO film before or after the step of directly bonding the graft polymer.

Moreover, in the manufacturing method of the electroconductive pattern material of this invention, it is preferable that the process of attaching an electroconductive material to a graft polymer consists of the method in any one of (1)-(4) mentioned below.
(1) A method of adsorbing conductive particles on a graft polymer.
(2) A method of performing electroless plating after adsorbing an electroless plating catalyst or a precursor thereof to a graft polymer.
(3) A method in which a metal ion or metal salt is adsorbed on the graft polymer, and then the metal ion in the metal ion or metal salt is reduced.
(4) A method of forming a conductive polymer layer by causing a polymerization reaction after adsorbing a conductive monomer to a graft polymer.

The PDP of the present invention is characterized in that the conductive pattern material obtained by the method for producing a conductive pattern material of the present invention is provided as a composite electrode.
Further, the liquid crystal display device of the present invention is a liquid crystal display device in which a driving IC chip is mounted on a substrate by a COG method, and the conductive pattern material obtained by the method for producing a conductive pattern material of the present invention is used. , And provided as input / output wiring of the drive IC chip.

According to the present invention, there is provided a conductive pattern material that can be applied to a laminated electrode or wiring that is excellent in adhesion and linearity between an ITO film and a metal film and that can be further refined, and a method for manufacturing the same. Can be provided.
In addition, according to the present invention, it is possible to provide a PDP that is provided with a conductive pattern material that constitutes a stacked electrode without disconnection or short circuit as a composite electrode, and that can achieve high definition.

Hereinafter, the present invention will be described in detail.
≪Conductive pattern material and method for producing conductive pattern material≫
The conductive pattern material of the present invention is characterized in that a graft polymer is directly bonded to the surface of an ITO film provided in a pattern on a substrate, and the conductive material is adhered to the graft polymer.
The method for producing a conductive pattern material of the present invention includes a step of providing an ITO film on a substrate (hereinafter referred to as “ITO film forming step” as appropriate) and a graft polymer directly bonded to the surface of the ITO film. A step (hereinafter referred to as “graft polymer generation step” as appropriate), a step of attaching a conductive material to the graft polymer (hereinafter referred to as “conductive material attachment step” as appropriate), and the graft polymer. Before or after the generating step, the method has a step of patterning the ITO film (hereinafter, referred to as “ITO film patterning step” as appropriate).
Hereinafter, since the process which passes through in order to obtain the electroconductive pattern material of this invention is the same as that of each process of the manufacturing method of the electroconductive pattern material of this invention, it demonstrates collectively below.

<ITO film formation process>
In this step, an ITO film is provided on the entire substrate surface. As this method, a conventionally known method can be applied. Specifically, first, a method of forming a film of ITO on a substrate by a sputtering method, an ion plating method, a vacuum evaporation method, a CVD method, or the like can be given.
The obtained ITO film is subjected to the following graft polymer generation step as it is or after being patterned (that is, after undergoing an ITO film patterning step described later).
Here, as a board | substrate with which an ITO film | membrane is provided, the glass substrate etc. which consist of glass, an alkali free glass, quartz glass etc. are mentioned, for example.

<Graft polymer production process>
In this step, any method may be used as long as a graft polymer can be generated on the ITO film surface.
In the present invention, after a compound having a polymerization initiating ability is bonded to the entire ITO film surface, energy is applied in a desired pattern to activate the polymerization initiating site of the compound, and that is the starting point. An embodiment in which a graft polymer is formed is preferably used.
This aspect will be described in detail.

Examples of the compound having a polymerization initiating ability applicable to this embodiment include a compound having a polymerization initiation site (Y) capable of initiating radical polymerization by photocleavage and an ITO binding site (Q) (hereinafter referred to as “photocleavage” as appropriate). Compound (QY) ") and the like.
Here, the polymerization initiation site where radical polymerization can be initiated by photocleavage (hereinafter simply referred to as “polymerization initiation site (Y)”) 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.
That is, aromatic ketone group, phenacyl ester group, sulfonimide group, sulfonyl ester group, N-hydroxysulfonyl ester group, benzylimide group, trichloromethyl group, benzyl chloride group, and the like.

When such a polymerization initiation site (Y) is cleaved by exposure and a radical is generated, when a polymerizable compound is present in the vicinity of the radical, this radical functions as a starting point for the graft polymerization reaction. Can be generated.
For this reason, when a graft polymer is generated on the surface of the ITO film having the photocleavable compound (QY) introduced on the surface, exposure at a wavelength capable of cleaving the polymerization initiation site (Y) is performed as an energy imparting means. It is necessary to use it.

  The ITO binding site (Q) is composed of a reactive group capable of reacting with and binding to the functional group (Z) present on the ITO film surface. Specific examples of the reactive group include the following: Groups as shown.

  The polymerization initiation site (Y) and the ITO 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 the compound (QY) having an ITO binding site (Q) and a polymerization initiation site (Y) are shown below together with the cleavage portion. It is not limited to.

Here, a hydroxyl group (functional group (Z)) originally exists on the surface of the ITO film used in the present invention due to its material. Therefore, the photocleavable compound (QY) is brought into contact with the ITO pattern, and the functional group (Z) present on the surface of the ITO pattern and the ITO binding site (Q) are bonded to the surface of the ITO pattern. The photocleavable compound (QY) is easily introduced.
The functional group (Z) present on the surface of the ITO film may be present on the surface of the ITO pattern surface by performing a surface treatment such as corona treatment.

As a specific method for bonding the photocleavable compound (QY) to the functional group (Z) present on the surface of the ITO film, the photocleavable compound (QY) is mixed with an appropriate solvent such as toluene, hexane, acetone or the like. Or a method in which the solution or dispersion is applied to the surface of the ITO film, or a method in which a substrate having the ITO film is immersed in the solution or dispersion may be applied. By these methods, an ITO film having a photocleavable compound (QY) introduced on the surface can be obtained.
At this time, the concentration of the photocleavable 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.

When the graft polymer is generated on the surface of the ITO film into which the photocleavable compound (QY) is obtained as described above, the graft polymer may be generated on the entire surface of the ITO film. A graft polymer may be formed on a part of the ITO film surface. That is, it is only necessary to generate the graft polymer only on the region on the ITO film surface where the metal film is to be formed.
As the method, a polymerizable compound is brought into contact with the surface of the ITO film, and pattern exposure is performed on the region where the metal film is to be formed, whereby the polymerization start site (Y) of the exposed portion is cleaved, and the graft polymer is started from there. Is used.

In addition, a graft polymer can be generated in a desired region on the surface of the ITO film by the following method.
First, the surface of the ITO film into which the photocleavable compound (QY) has been introduced is subjected to pattern exposure in advance along the region where the graft polymer is not desired to be generated, and the compound (QY) bonded to the ITO film surface. ) Is photocleavaged to deactivate the polymerization initiating ability. Thereby, a polymerization startable region and a polymerization initiating ability deactivated region are formed on the surface of the ITO film. Then, after bringing the polymerizable compound into contact with the ITO film surface on which the polymerization startable region and the polymerization initiating ability deactivation region are formed, the entire surface is exposed (exposing the entire ITO surface), thereby allowing the polymerization startable region. As a result, a graft polymer is formed only in the region, and as a result, a graft polymer is formed in a desired region on the surface of the ITO film.
In the present invention, there is a region (substrate surface exposed portion) where the ITO film is not formed on the surface of the substrate, and the photocleavable compound (QY) is also introduced into the substrate exposed surface. When it exists, it can prevent that a graft polymer is produced | generated in the location where it is not desired by performing pattern exposure as mentioned above and deactivating polymerization initiation ability.

  In order to produce a graft polymer as described above, in the present invention, an ITO film into which a photocleavable compound (QY) is introduced in a state where a polymerizable compound is used alone or dispersed or dissolved in a solvent. It is necessary to contact the surface. As this contact method, a substrate having an ITO film may be immersed in a liquid composition containing a polymerizable compound, but from the viewpoint of handleability and production efficiency, the polymerization is performed on the surface of the ITO film. A method of forming a coating film by contacting the polymerizable compound as it is or by applying a liquid composition containing a polymerizable compound, and further drying the coating film to contain a layer containing the polymerizable compound on the ITO film surface ( It is preferably carried out by forming a graft polymer precursor layer).

(Polymerizable compound)
Next, the polymerizable compound used in the present invention will be described.
As the polymerizable compound used in the present invention, any of a monomer, a macromonomer, and a polymer compound having a polymerizable group can be used. As these polymerizable compounds, known compounds can be arbitrarily used.
Among these, the polymerizable compound particularly useful in the present invention is appropriately selected depending on the mode used in the conductive material adhesion step described later. In other words, in order to hold the conductive material efficiently, easily and at a high density with respect to the generated graft polymer, functional groups that can directly interact with the conductive material or the conductive material are efficiently held. It is preferable to use a polymerizable compound having a functional group capable of forming an interaction with the material used for the purpose.
Hereinafter, the functional group that can directly interact with the conductive material and the functional group that can form an interaction with the material used for efficiently holding the conductive material will be generally described as an interactive group.
Examples of the interactive group include a polar group. Among these polar groups, a hydrophilic group is preferable, and more specifically, a negatively charged group such as a functional group having a positive charge such as ammonium or phosphoni, a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phossonic acid group. In addition to the functional group having a non-ionic group, for example, a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, a cyano group, and the like can be given.
Hereinafter, the polymerizable compound having an interactive group that is preferably used in the graft polymer production step will be described in detail.

  Specific examples of the monomer as the polymerizable compound having an interactive group that can be used in the present invention include (meth) acrylic acid or an alkali metal salt and amine salt thereof, itaconic acid or an alkali metal salt and amine salt thereof. Styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethyl (meth) acrylate or its alkali metal salt and amine salt, 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salt and amine salt, acid phospho Oxypolyoxyethylene glycol mono (meth) acrylate or alkali metal salts and amine salts thereof, polyoxyethylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylo (Meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, N-vinylpyrrolidone, vinylimidazole, vinylpyridine, vinylthiophene, styrene, ethyl (meth) acrylate, n-butyl Examples include (meth) acrylic acid esters having an alkyl group having 1 to 24 carbon atoms such as (meth) acrylic acid esters.

The macromonomer as the polymerizable compound having an interactive group that can be used in the present invention can be prepared by a known method using the monomer. The method for producing the macromonomer used in this embodiment is described in, for example, Chapter 2 of “Macromonomer Chemistry and Industry” (Editor, Yuya Yamashita) published on September 20, 1999, published by the IP Publishing Department. Various production methods have been proposed in “Synthesis”.
The useful weight average molecular weight of such a macromonomer is in the range of 500 to 500,000, with a particularly preferred range being 1000 to 50,000.

The polymer compound as the polymerizable compound having an interactive group that can be used in the present invention is an interactive group and an ethylene addition polymerizable unsaturated group (polymerization) such as a vinyl group, an allyl group, or a (meth) acryl group. A functional group). This polymer has an ethylene addition polymerizable unsaturated group at least at the terminal or side chain, more preferably has an ethylene addition polymerizable unsaturated group at the side chain, and has no ethylene addition polymerizable unsaturated group at the terminal and side chain. Those having a saturated group are more preferred.
The useful weight average molecular weight of such a polymer compound is in the range of 500 to 500,000, and a particularly preferred range is 1000 to 50,000.

As a method for synthesizing a polymer compound having an interactive group and a polymerizable group, i) a method of copolymerizing a monomer having an interactive group and a monomer having a polymerizable group, ii) an interactive group A monomer having a polymerizable group precursor and a monomer having a polymerizable group precursor, and then introducing a double bond by treatment with a base or the like, iii) a polymer having an interactive group and a monomer having a polymerizable group The method of making it react and introduce | transducing a polymeric group is mentioned.
A preferred synthesis method is, from the viewpoint of synthesis suitability, ii) a method of copolymerizing a monomer having an interactive group and a monomer having a polymerizable group precursor, and then introducing a polymerizable group by treatment with a base, iii) A method of introducing a polymerizable group by reacting a polymer having an interactive group with a monomer having a polymerizable group.

  Examples of the monomer having an interactive group used in the synthesis methods i) and ii) include (meth) acrylic acid or an alkali metal salt and amine salt thereof, itaconic acid or an alkali metal salt and amine salt thereof, and the like. Specifically, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or a hydrohalide thereof, 3-vinylpropionic acid Or alkali metal salts and amine salts thereof, vinylsulfonic acid or alkali metal salts and amine salts thereof, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, Ashi Examples thereof include phosphooxypolyoxyethylene glycol mono (meth) acrylate, N-vinylpyrrolidone (the following structure), sodium styrenesulfonate, vinylbenzoic acid, and the like. Generally, carboxyl group, sulfonic acid group, phosphoric acid group, A monomer having an amino group or a salt thereof, a hydroxyl group, an amide group, a phosphine group, an imidazole group, a pyridine group, or a salt thereof, or a functional group such as an ether group can be used.

Examples of the monomer having a polymerizable group that is copolymerized with the monomer having an interactive group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Moreover, as a monomer which has a polymeric group precursor used for the synthetic | combination method of said ii), 2- (3-chloro- 1-oxopropoxy) ethyl methacrylate [*], and Unexamined-Japanese-Patent No. 2003-335814 are described. Compounds (i-1 to i-60) can be used, and among these, the following compound (i-1) is particularly preferable.

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

  Regarding the method of introducing a polymerizable group by treatment with a base after copolymerizing a monomer having an interactive group and a monomer having a polymerizable group precursor in the synthesis method of ii), for example, The method described in JP2003-335814A can be used.

The solvent constituting the liquid composition containing these polymerizable compounds is not particularly limited as long as the polymerizable compound as a main component can be dissolved or dispersed, but an aqueous solvent such as water or a water-soluble solvent. It is preferable that a surfactant may be further added to the mixture or the solvent.
Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone and cyclohexanone, amides such as formamide and dimethylacetamide. System solvents, and the like.

  Further, the surfactant that can be added to the liquid composition as necessary may be any one that dissolves in a solvent. Examples of such a surfactant include n-dodecylbenzenesulfonic acid. Anionic surfactants such as sodium, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxy Examples include ethylene sorbitan monolaurate (commercially available products such as “Tween 20”) and nonionic surfactants such as polyoxyethylene lauryl ether.

When a method of forming a coating film by applying a liquid composition containing a polymerizable compound to the ITO film surface is used, the coating amount is 0 in terms of solid content from the viewpoint of obtaining a sufficient coating film. .1 to 10 g / m ² is preferable, and 0.5 to 5 g / m ² is particularly preferable.
Further, the film made of the resulting graft polymer (graft polymer layer) is preferably having a thickness in the range of 0.1 to 2.0 g / m ^2, more preferably 0.3 to 1.0 g / m ² The most preferable range is 0.5 to 1.0 g / m ² .

(exposure)
In this step, the pattern exposure for generating the graft polymer, the pattern exposure performed for deactivating the polymerization initiating ability, and the entire surface exposure performed for generating the graft polymer are all performed at the polymerization initiation site ( The exposure is not particularly limited as long as it can cause cleavage in Y), and may be exposure with ultraviolet rays or exposure with visible light.
Examples of the light source used for exposure include ultraviolet light, deep ultraviolet light, visible light, and laser light. Specifically, excimer lasers such as ultraviolet light, i-line, g-line, KrF, and ArF are used. Among these, i-line, g-line, and excimer laser are preferable.

The pattern resolution formed by the present invention depends on the exposure conditions. That is, a high-definition pattern corresponding to the exposure is formed by performing high-definition pattern exposure in pattern exposure for generating the graft polymer or pattern exposure performed for deactivating the polymerization initiating ability. Examples of the exposure method for forming a high-definition pattern include light beam scanning exposure using an optical system, exposure using a mask, and the like, and an exposure method corresponding to the resolution of a desired pattern may be taken.
Specific examples of the high-definition pattern exposure include stepper exposure such as i-line stepper, g-line stepper, KrF stepper, and ArF stepper.
The pattern shape in the pattern exposure is selected according to the desired shape of the metal film.

  After the graft polymer is generated as described above, the substrate having the graft polymer generation surface is subjected to treatments such as solvent immersion and solvent washing, and the remaining homopolymer is removed and purified. Specifically, washing with water or acetone, drying and the like can be mentioned. From the viewpoint of homopolymer removability, means such as ultrasonic waves may be taken. In the purified substrate, the homopolymer remaining on the surface is completely removed, and only the graft polymer firmly bonded to the ITO substrate is present.

  As described above, the graft polymer is directly bonded to a desired region on the surface of the ITO film, and then a conductive material attaching step is performed.

<Conductive material adhesion process>
In this step, a conductive material is attached to the graft polymer to form a conductive pattern formed by laminating an ITO film and a metal film. Specific methods include the following four aspects.
The first aspect is a method of forming a conductive particle adsorption layer by adsorbing conductive particles to an interactive group (ionic group) of a graft polymer.
The second aspect is a method of forming a plating film by performing electroless plating after adsorbing an electroless plating catalyst or a precursor thereof to an interactive group of a graft polymer.
A third aspect is a method in which a metal ion or metal salt is adsorbed to the interactive group of the graft polymer, and then the metal ion in the metal ion or metal salt is reduced to form a metal fine particle dispersed film. is there.
A fourth aspect is a method of forming a conductive polymer layer by causing a polymerization reaction to occur after adsorbing a conductive monomer to an interactive group of a graft polymer.
Hereinafter, the first to fourth aspects will be described.

(First aspect: formation of conductive particle adsorption layer)
In the first aspect of the conductive material adhesion step, the conductive particles described below are adsorbed ionically according to their polarities with respect to the interactive group of the graft polymer, particularly preferably the ionic group. And forming a conductive particle adsorption layer. By this method, a conductive pattern composed of an ITO film and a conductive particle adsorption layer is formed.
The conductive particles adsorbed here form an interaction layer with the graft polymer interaction group and are fixed in a monomolecular film state or a multilayer state to form a conductive particle adsorption layer. In addition to being excellent in adhesion to the conductive particle adsorption layer, it has the advantage that sufficient conductivity can be expressed.

The conductive particles that can be applied to the first embodiment 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.
These conductive particles are 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.

-Relationship between polarity of ionic groups (interactive groups) of graft polymer and conductive particles-
When the graft polymer obtained in the present invention has an anionic interactive group such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group, the interactive group of the graft polymer is selectively negatively charged. It is possible to adsorb (cationic) conductive particles having a positive charge.

  Examples of such cationic conductive particles include positively charged metal (oxide) fine particles. Fine particles having a high density and positive charge on the surface can be obtained by, for example, the method of Toru Yonezawa et al. Yonezawa, Chemistry Letters. 1999 page 1061, T. et al. Yonezawa, Langumuir 2000, vol 16, 5218 and Toru Yonezawa, Polymer preprints, Japan vol. 49.2911 (2000). Yonezawa et al. Show that metal particle surfaces that are chemically modified with a functional group having a positive charge at high density can be formed using metal-sulfur bonds.

On the other hand, when the obtained graft polymer has an interactive group such as an ammonium group described in JP-A-10-296895, the interactive group of the graft polymer selectively has a positive charge. The conductive particles having a negative charge can be adsorbed here.
Examples of negatively charged conductive particles include gold or silver particles obtained by citric acid reduction.

  The particle size of the conductive particles used in the present invention is preferably in the range of 0.1 nm to 1000 nm, preferably in the range of 1 nm to 100 nm, from the viewpoint of adsorptivity to the interactive group and the expression of conductivity. Is more preferable.

As a method for adsorbing the conductive particles to the interactive group of the graft polymer, a method in which a solution in which conductive particles having a charge are dissolved or dispersed on the surface is applied to the graft polymer generation region, and these The method of immersing the board | substrate with which the graft polymer was produced | generated in a solution or a dispersion liquid etc. are mentioned.
In either case of application or immersion, an excessive amount of conductive particles is supplied and introduced by sufficient ionic bonds with the interactive group (ionic group). The contact time with the graft polymer generation surface is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.
Further, these conductive particles are preferably bonded in the maximum amount that can be adsorbed to the interactive group of the graft polymer from the viewpoint of durability and ensuring the conductivity, in which case the dispersion concentration of the dispersion is 0.001 to 20% by mass is preferable.

Further, in the first aspect of the conductive material attaching step, it is preferable to heat the entire substrate after the conductive particles are adsorbed to the graft polymer. By performing this heating, fusion occurs between the attached conductive particles, and the adhesion between the conductive particles can be improved and the conductivity can be increased.
Here, as temperature in a heating process, 50 to 500 degreeC is preferable, More preferably, it is 100 to 300 degreeC, Most preferably, it is 150 to 300 degreeC.

(Second aspect: formation of plating film)
In the second aspect of the conductive material adhesion step, the electroless plating catalyst or its precursor is adsorbed to the interactive group of the graft polymer after the electroless plating catalyst or its precursor is adsorbed to the interactive group of the graft polymer. And forming a plating film. By this method, a conductive pattern composed of an ITO film and a plating film is formed.
Thus, since the plating film is formed by electroless plating with respect to the catalyst or precursor adsorbed on the interactive group of the graft polymer, the plating film and the graft polymer are firmly bonded. As a result, the adhesiveness between the ITO film and the plating film is excellent, and the conductivity can be adjusted according to the plating conditions.

First, the method for applying the electroless plating catalyst or precursor thereof in the second embodiment will be described.
The electroless plating catalyst used in this embodiment is mainly a zero-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable because of their good handleability and high catalytic ability. As a technique for fixing the zero-valent metal to the interaction region, for example, a technique in which a metal colloid whose charge is adjusted so as to interact with the interaction group of the graft polymer is used on the surface of the graft polymer is used. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here, and the metal colloid whose charge is adjusted in this way interacts with the interactive group of the graft polymer. A metal colloid (electroless plating catalyst) can be attached to the graft polymer.

  The electroless plating catalyst precursor used in this embodiment can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. After the metal ion, which is an electroless plating catalyst precursor, is applied to the graft polymer formation region, it may be converted into a zero-valent metal by a reduction reaction before immersion in the electroless plating bath. Alternatively, the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

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

  As a method of applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor to a graft polymer, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is dissolved in an appropriate solvent. Then, a solution containing dissociated metal ions is prepared, and the solution is applied to the graft polymer generation region, or the substrate on which the graft polymer is generated 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.

Next, the electroless plating method in the second aspect will be described.
An electroless plating film is formed by performing electroless plating on the graft polymer to which the electroless plating catalyst or its precursor is applied.
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
The electroless plating in this step is performed, for example, by rinsing a substrate provided with an electroless plating catalyst to remove excess electroless plating catalyst (metal) and then immersing it in an electroless plating bath. As the electroless plating bath 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 contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate, and sodium succinate as complexing agents. It is included. Further, the electroless plating bath of palladium contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

  The film thickness of the electroless plating film thus formed can be controlled by the concentration of metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, etc. In view of the above, it is preferably 0.5 μm or more, and more preferably 3 μm or more. Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

  In the electroless plating film obtained as described above, fine particles of the electroless plating catalyst and plating metal are firmly dispersed in the graft polymer film by cross-sectional observation by SEM, and further, relatively large particles are further formed thereon. Precipitation was confirmed. Since the interface is a hybrid state of the graft polymer and fine particles, the adhesion between the substrate (organic component) and the inorganic substance (electroless plating catalyst or plating metal) was good.

Further, in the second aspect of the conductive material adhesion step, electroplating can be performed after the electroless plating is completed. That is, the electroplating is performed using the electroless plating film obtained by the above electroless plating as an electrode. As a result, it is possible to easily form a new plating film having an arbitrary thickness on the basis of the electroless plating film having excellent adhesion with the ITO film. By adding this step, the conductive film can be formed to a thickness according to the purpose.
As the electroplating method in this embodiment, a conventionally known method can be used. In addition, as a metal used for electroplating, copper, chromium, lead, nickel, gold | metal | money, silver, tin, zinc etc. are mentioned, Copper, gold | metal | money, silver is preferable from a conductive viewpoint, and copper is more preferable.

  The thickness of the plating film obtained by electroplating varies depending on the application, and can be controlled by adjusting the concentration of metal contained in the plating bath, the immersion time, or the current density. In addition, when using the surface conductive material obtained by this invention when producing a printed wiring board, it is preferable that the film thickness of a plating film is 0.3 micrometer or more from a conductive viewpoint, and is 3 micrometers or more. It is more preferable that

(Third embodiment: Formation of metal fine particle dispersion film)
According to a third aspect of the conductive material adhesion step, a metal ion or a metal salt described below is ionic depending on the polarity of the interactive group of the graft polymer, particularly preferably the ionic group. Then, the metal ions in the metal salt or the metal salt are reduced to precipitate a metal simple substance to form a metal fine particle dispersed film. The metal fine particle dispersed film may be a metal thin film depending on the precipitation mode of the metal simple substance. By this method, a conductive pattern composed of an ITO film and a metal fine particle dispersed film is formed.
Here, the deposited metal fine particles forming the metal fine particle dispersed film form an interaction with the interacting group of the graft polymer and adsorb, so that the adhesion between the ITO film and the metal fine particle dispersed film is improved. In addition to being excellent, it has an advantage that sufficient conductivity can be expressed.

(Metal ions and metal salts)
First, metal ions and metal salts used in this embodiment will be described.
In the present invention, the metal salt is not particularly limited as long as it is dissolved in an appropriate solvent and can be dissociated into a metal ion and a base (anion) in order to impart it to the formation region of the graft polymer. (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 Ag, Cu, Al, Ni, Co, Fe, and Pd. Among these, Ag and Cu are preferable.
Not only one kind of metal salt and metal ion but also a plurality of kinds can be used in combination as required. In order to obtain desired conductivity, a plurality of materials can be mixed and used in advance.

(Method for applying metal ions and metal salts)
When a metal ion or a metal salt is imparted to the graft polymer, (1) when the graft polymer has an ionic group, a method of adsorbing the metal ion to the ionic group is used. In this case, the above metal salt is dissolved in an appropriate solvent, and the solution containing the dissociated metal ions is applied to the region where the graft polymer is formed, or the substrate where the graft polymer is generated is immersed in the solution. That's fine. 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 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. 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) if the graft polymer has a high affinity for the metal salt, such as polyvinylpyrrolidone, the metal salt is directly attached in the form of fine particles, or If a dispersion is prepared using an appropriate solvent in which the metal salt can be dispersed, and the dispersion is applied to the region where the graft polymer is produced, or the substrate where the graft polymer is produced is immersed in the solution. Good.
When the graft polymer has a hydrophilic group as an interactive group, the graft polymer film has high water retention. Therefore, using the high water retention, the dispersion in which the metal salt is dispersed in the graft polymer film. It is preferable to impregnate. From the viewpoint of sufficiently performing the impregnation of the dispersion, the metal salt concentration of the dispersion 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. The contact time is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.

When a metal ion or a metal salt is applied to the graft polymer, (3) when the graft polymer has a hydrophilic group, a dispersion in which the metal salt is dispersed or a solution in which the metal salt is dissolved is used as a graft polymer generation region. Or a substrate on which a graft polymer is formed may be immersed in the dispersion or solution.
Also in such a method, similarly to the above, the graft polymer film can be impregnated with the dispersion or solution by utilizing the high water retention property of the graft polymer film. From the viewpoint of sufficiently impregnating the dispersion or solution, the metal ion concentration or 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.
In particular, according to the method (3), a desired metal ion or metal salt can be imparted regardless of the properties of the interactive group of the graft polymer.

(Reducing agent)
Subsequently, the metal salt present by adsorbing or impregnating the graft polymer (membrane) or the reducing agent used for reducing metal ions will be described.
The reducing agent used in the present invention is not particularly limited as long as it has physical properties that reduce metal ions and precipitate a single metal, and examples thereof include hypophosphites, tetrahydroborates, and hydrazines. .
These reducing agents can be appropriately selected in relation to the metal salt and metal ion to be used. For example, when a silver nitrate aqueous solution or the like is used as the metal salt aqueous solution for supplying the metal ion or metal salt, tetrahydroboron is used. When sodium acid uses an aqueous palladium dichloride solution, hydrazine is preferred.

  As the method for adding the reducing agent, for example, a metal ion or a metal salt is added to the surface of the substrate on which the graft polymer has been formed, and then washed with water to remove excess metal salt or metal ion, and then the surface is provided. Examples include a method of immersing the 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 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.

Here, the relationship between the interactive group of the graft polymer and the metal ion or metal salt in the third embodiment will be described.
When the graft polymer interacting group is a negatively charged polar group or an anionic ionic group such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group, the graft polymer membrane is selectively used. Since it has a negative charge, metal ions having a positive charge are adsorbed here, and the adsorbed metal ions are reduced to deposit a single metal.
In addition, when the interactive group of the graft polymer is an ionic group of a cationic group such as an ammonium group described in JP-A-10-296895, the graft polymer film selectively has a positive charge. Thus, the metal ions are not adsorbed as they are. Therefore, utilizing the hydrophilicity resulting from the ionic group of the interactive group, the graft polymer film is impregnated with a dispersion in which the metal salt is dispersed or a solution in which the metal salt is dissolved, and the impregnated solution The metal simple substance is precipitated by reducing the metal ion in the metal or the metal ion in the metal salt.
As described above, the metal fine particle dispersion film is formed by precipitation of the metal simple substance.

Presence of the deposited metal simple substance (metal fine particles) in the metal fine particle dispersed film can be visually confirmed by the metallic luster of the surface, but using a transmission electron microscope or AFM (atomic force microscope). By observing the surface, the structure (form) can be confirmed. The metal pattern can be easily formed by a conventional method, for example, a method of observing the cut surface with an electron microscope.
Thus, when the state in which the metal simple substance precipitated is observed with the above-mentioned microscope, it is confirmed that the metal fine particles are firmly dispersed in the graft polymer film. At this time, the size of the deposited metal fine particles is about 1 μm to 1 nm in particle size.

In the metal fine particle dispersion film, when the metal fine particles are densely dispersed and apparently form a metal thin film, it may be used as it is, but from the viewpoint of ensuring efficient conductivity, It is preferable to further heat-treat the fine particle dispersed film.
The heating temperature in the heat treatment step is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably about 200 ° C. The heating temperature is preferably 400 ° C. or lower in consideration of the processing efficiency and the dimensional stability of the 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.

(Fourth aspect: formation of conductive polymer layer)
In a fourth aspect of the conductive material adhesion step, the conductive monomer described below is ionically adsorbed to the interactive group of the graft polymer, particularly preferably the ionic group, and then polymerized as it is. In this method, a conductive polymer layer is formed by causing a reaction. By this method, a conductive pattern composed of an ITO film and a conductive polymer layer is formed.
Here, the conductive polymer layer is formed by polymerizing an interactive group of the graft polymer and the ionically adsorbed conductive monomer, so that it has excellent adhesion and durability with the ITO film, and the monomer supply rate, etc. By adjusting the polymerization reaction conditions, 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 A polymerization reaction between them proceeds, and an extremely thin film of a conductive polymer is formed in a region where a graft polymer is formed on the substrate. Thereby, a uniform and thin conductive polymer layer is obtained.

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

In the present invention, the conductive monomer itself is strongly adsorbed by forming an interaction with the graft polymer interacting group electrostatically or polarly. Since the polymer layer forms a strong interaction with the region where the graft polymer is formed, 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. Thus, since it functions as a kind of dopant, it is possible to obtain an effect that the conductivity of the conductive polymer layer (conductive pattern) 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 graft polymer generation region and the conductive polymer are obtained by the interaction between the two. Polythiophene having a sulfonic acid group (sulfo group) exists as a counter anion at the interface with the layer, 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 production | generation area | region surface of a graft polymer, 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. preferable. 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.

<ITO film patterning process>
In this step, the ITO film provided on the substrate surface is patterned. This step may be performed before or after the graft polymer generation step described above.
That is, when this step is performed before the graft polymer generation step, only the ITO film provided on the substrate surface is patterned into a desired wiring or electrode shape.
On the other hand, when performing this process after a graft polymer production | generation process, there exist the following two aspects. The first is an embodiment in which the graft polymer is bonded (generated) to the entire surface of the ITO film provided on the substrate surface. In this case, the ITO film is patterned together with the bonded graft polymer. The second is an embodiment in which the graft polymer is bonded (generated) only to a desired region on the surface of the ITO film provided on the substrate surface. In this case, the patterning of the ITO film is performed using the graft polymer. The pattern shape is equal to or larger than the combined (generated) region.
In addition, this process can also be performed after the conductive material adhesion process described above.
Although the patterning of the ITO film has been described above, it is preferable to use a photolithography process and an etching process for this patterning.

As described above, the conductive pattern in the present invention is formed, and the conductive pattern material of the present invention is obtained.
The conductive pattern obtained as described above can obtain the shape and resolution of the patterned ITO film and the shape and resolution corresponding to the pattern exposure when generating the graft polymer. The conductive pattern material (conductive pattern material of the present invention) obtained by the method for producing a conductive pattern material can be made highly precise and has excellent linearity.
In addition, the conductive particle adsorption layer, the plating film, the metal fine particle dispersion film, and the conductive polymer layer described above are uniformly and strongly applied to the graft polymer bonded to the ITO film. Since they are bonded, the adhesion between the conductive expression layer and the ITO film is excellent, the problem of disconnection does not occur, and uniform conductivity can be obtained.
Furthermore, as described above, this conductive pattern material does not require a metal film etching step as in the prior art, and can prevent a short circuit between wirings due to the remaining metal film.

  The conductive pattern material (conductive pattern material of the present invention) obtained by the method for producing the conductive pattern material of the present invention is particularly suitable as a composite electrode in the front glass substrate of the PDP shown below, It is also suitable as an input / output wiring of the driving IC chip in a liquid crystal display device in which the driving IC chip is mounted by the COG method.

≪PDP≫
The PDP of the present invention is characterized by comprising the above-described conductive pattern material of the present invention as a composite electrode in a front glass substrate.
The PDP of the present invention is not limited as long as it includes a front glass substrate provided with a composite electrode to which the conductive pattern material of the present invention is applied, a rear glass substrate opposed to the front glass substrate, and a transparent dielectric layer between both substrates. It may be a thing. One embodiment of the PDP of the present invention will be described with reference to FIG. Here, FIG. 1 is a partially exploded perspective view showing a configuration of a surface discharge type AC side PDP provided with a composite electrode to which the conductive pattern material of the present invention is applied.

As shown in FIG. 1, the PDP 100 includes a front glass substrate 10, a rear glass substrate 20, and a transparent dielectric layer 30 and a protective layer 40 sandwiched between both substrates 10 and 20.
The front glass substrate 10 has a display electrode (composite electrode) 15 comprising a transparent ITO electrode 13 for discharging and a bus electrode 14 for lowering the line resistance of the transparent ITO electrode on the surface of the glass substrate 11 at a predetermined pitch. It is arranged in multiple rows. In the present invention, the display electrode (composite electrode) 15 is formed of a conductive pattern. A black matrix 12 is provided on the surface of the glass substrate 11 in parallel with the display electrodes 15. Further, a transparent dielectric layer (low melting point glass) 30 for accumulating charges is formed by printing and baking adjacent to the display electrode 15, and a protective layer (MgO) 40 is deposited thereon. The protective layer 40 has a role of protecting the display electrode 15 and maintaining a discharge state.
On the other hand, the rear glass substrate 20 has a plurality of rows of striped ribs (partitions) 22 partitioning the discharge space and address electrodes 23 arranged in each discharge space on the surface of the glass substrate 21 at a predetermined pitch. Has been. Further, phosphor films of three colors of red (24a), blue (24b), and green (24c) are regularly arranged on the inner surface of each discharge space.
In the PDP 100, one pixel is configured by phosphor films 24a, 24b, and 24c of three primary colors of red, blue, and green in full color display.

As described above, since the conductive pattern material of the present invention can increase the definition of the conductive pattern and has good adhesion, the conductive pattern material is provided as a display electrode (composite electrode). High definition can also be achieved as a PDP.
In addition, the conductive pattern in the conductive pattern material of the present invention does not require an etching process or the like when forming a patterned metal film, and therefore can be easily applied to an increase in the size of the display electrode (composite electrode). Therefore, the range of selection of the size of the PDP itself is not reduced.

≪Liquid crystal display device≫
A liquid crystal display device suitable for the use of the conductive pattern material of the present invention is a liquid crystal display device in which a drive IC chip is mounted on a substrate by a COG method, and the conductive pattern material of the present invention is used for the drive. It is preferable to provide as an input / output wiring of an IC chip.
Such a liquid crystal display device may be any device as long as the driving IC chip is mounted on the substrate by the COG method. One mode of the liquid crystal display device according to the present invention will be described with reference to FIG. Here, FIG. 2 is a schematic diagram showing a configuration of a simple matrix type liquid crystal display device (LCD) provided with the conductive pattern material of the present invention as input / output wirings of a driving IC chip.

As shown in FIG. 2, in the liquid crystal display device 200, drive IC chips 52A, 52B, and 52C (here, an example in which three chips are schematically arranged) mounted on the peripheral portion 51 of the LCD panel substrate 50 are shown. Are connected by an input / output wiring 53.
In the present invention, the input / output wiring 53 of the drive IC chips 52A, 52B, 52C is preferably formed of a conductive pattern. Here, 50 denotes an LCD liquid crystal panel substrate, and 54 denotes an FPC (flexible printed circuit).
Here, a simple matrix LCD has been described as an example. However, the present invention is not limited to this, and the formation of the conductive pattern (wiring) according to the present invention can be widely applied to applications that require a reduction in resistance of ITO wiring or other metal wiring. Needless to say.

As described above, since the conductive pattern material of the present invention can increase the definition of the conductive pattern and has good adhesion, this conductive pattern material is used as the input / output wiring of the driving IC chip. High definition can also be achieved as a liquid crystal display element provided.
In addition, since the conductive pattern in the conductive pattern material of the present invention does not require an etching process or the like when forming the patterned metal film, the input / output wiring of the driving IC chip accompanying the enlargement of the liquid crystal display device It is possible to easily cope with longer distances.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
[Example 1]
(Formation of ITO pattern)
An ITO film having a thickness of 0.1 μm was formed on a glass substrate (manufactured by Nippon Sheet Glass Co., Ltd.). Then, a dry photoresist was used to form a resist pattern on the ITO film. Thereafter, etching was performed to form an ITO pattern.

(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 DMAc 50 g and THF 50 g, 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.

¹ H 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.

¹ H 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) )

(Binding of photocleavable compounds)
The glass substrate on which the ITO pattern was formed 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 dehydrated toluene solution of 12.5% by mass of Compound A for 1 hour. After taking out, it wash | cleaned in order with toluene, acetone, and a pure water. Thus, the board | substrate with which the photocleavable compound was introduce | transduced into the ITO pattern surface was obtained.

(Generation of graft polymer)
Next, 5 ml of a 20% by mass aqueous solution of acrylic acid was dropped on the surface of the substrate on which the ITO pattern was formed, and a quartz plate was placed thereon, and the aqueous solution was uniformly sandwiched between the substrate and the quartz plate. On the quartz plate, a pattern mask (NC-1, manufactured by Toppan Printing Co., Ltd.) that transmits light in the same shape as the ITO pattern is fastened with a clip, and an exposure machine (UVX-02516S1LP01, manufactured by USHIO INC.) For 1 minute. After the exposure, the quartz plate and the mask were removed and washed thoroughly with pure water.
As described above, a substrate having a graft polymer made of acrylic acid bonded to the entire ITO pattern surface was obtained.

(Adhesion of conductive material)
The obtained substrate was immersed in a 0.1% by mass aqueous solution of palladium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 hour, and then washed with distilled water. Then, it was immersed in an electroless plating bath having the following composition for 20 minutes to obtain a Cu plating film.

<Electroless plating bath components>
・ OPC Kappa-H T1 (Okuno Pharmaceutical Co., Ltd.) 6mL
・ OPC Kappa-H T2 (Okuno Pharmaceutical Co., Ltd.) 1.2mL
・ OPC Kappa-H T3 (Okuno Pharmaceutical Co., Ltd.) 10mL
・ Water 83mL

When the obtained Cu plating film was observed using an optical microscope (manufactured by Nikon, OPTI PHOTO-2), a good conductive pattern in which the Cu plating film was laminated on the ITO pattern was confirmed.
Further, when the surface conductivity of the conductive pattern formed by laminating the Cu plating film on the ITO film was measured by the four-probe method using LORESTA-FP (manufactured by Mitsubishi Chemical Corporation), it was 0.3Ω / □. there were.
Further, the surface of the conductive pattern was rubbed 20 times by hand using a cloth (BEMCOT, manufactured by Asahi Kasei Kogyo Co., Ltd.) moistened with water. After rubbing, when observed with an optical microscope in the same manner as described above, a good conductive pattern similar to that before the rubbing treatment was confirmed. Moreover, there was no change in surface conductivity.

From the above, it has been found that the conductive pattern material in Example 1 has a conductive pattern that is excellent in conductivity and that has excellent adhesion between the ITO film and the Cu plating film (metal film). did.
From these things, it is easy to apply this conductive pattern material to the laminated wiring and electrode of an ITO film and a metal film. Therefore, it can be widely applied to various uses.

It is a partial exploded perspective view which shows the structure of AC side PDP of the surface discharge system provided with the composite electrode to which the electroconductive pattern material of this invention is applied. It is a schematic diagram showing a configuration of a simple matrix type liquid crystal display device (LCD) provided with the conductive pattern material of the present invention as input / output wiring of a driving IC chip.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Front glass substrate 11 Glass substrate 12 Black matrix 13 Transparent electrode 14 Bus electrode 15 Display electrode 20 Back glass substrate 21 Glass substrate 22 Rib (partition)
23 Data electrode for PDP (address electrode)
24a, 24b, 24c Phosphor film 30 Transparent dielectric layer 40 Protective layer 50 LCD panel substrate 51 Peripheral portion of LCD panel substrate 52A, 52B, 52C Driving IC chip 53 Input / output wiring of driving IC chip 54 FPC (flexible printed) ·circuit)
100 PDP
200 Liquid crystal display device

Claims (7)

  A conductive pattern material comprising a graft polymer directly bonded to a surface of an ITO film provided in a pattern on a substrate, and a conductive material attached to the graft polymer. Providing an ITO film on the substrate;
Directly bonding the graft polymer to the surface of the ITO film;
Attaching a conductive material to the graft polymer;
Have
A method for producing a conductive pattern material, comprising a step of patterning the ITO film before or after the step of directly bonding the graft polymer.   The method for producing a conductive pattern material according to claim 2, wherein the step of attaching the conductive material to the graft polymer uses a method of adsorbing conductive particles to the graft polymer.   3. The method according to claim 2, wherein the step of attaching a conductive material to the graft polymer uses a method of performing electroless plating after adsorbing an electroless plating catalyst or a precursor thereof to the graft polymer. A method for producing a conductive pattern material.   The step of attaching a conductive material to the graft polymer uses a method in which a metal ion or a metal salt is adsorbed on the graft polymer and then the metal ion in the metal ion or the metal salt is reduced. Item 3. A method for producing a conductive pattern material according to Item 2.   3. The method of attaching a conductive material to the graft polymer uses a method of forming a conductive polymer layer by causing a polymerization reaction after adsorbing a conductive monomer to the graft polymer. The manufacturing method of the electroconductive pattern material of description.   A PDP comprising a conductive pattern material obtained by the method for producing a conductive pattern material according to any one of claims 2 to 6 as a composite electrode.

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