JP2006064923A - Method for producing conductive pattern material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a conductive pattern material with a conductive pattern having high resolution, no break and excellent durability. <P>SOLUTION: The method for producing the conductive pattern material comprises: a step of directly bonding a graft polymer having functional groups capable of interacting with conductive particles and crosslinkable functional groups to a top of a base material in a pattern shape; a step of forming a conductive particle adsorbed layer by adsorbing conductive particles on the functional groups capable of interacting with the conductive particles in the graft polymer; and a step of forming a crosslinked structure in the conductive particle adsorbed layer by applying energy to the conductive particle adsorbed layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a conductive pattern material, and more particularly to a method for producing a conductive pattern material useful as a printed wiring board or the like.

Conventionally, various conductive pattern materials have been used for the formation of wiring boards. A typical example of these is that a thin film conductive material formed by a known method such as vacuum deposition is provided on an insulator, which is subjected to resist treatment, and a part of the resist prepared in advance is removed by pattern exposure. Then, what performs an etching process and forms a desired pattern is mentioned (for example, refer patent document 1). In such a method, at least four steps are required, and when the wet etching process is performed, a treatment process of the waste liquid is also required, and thus a complicated process has to be taken.
As another conductive pattern forming method, a method using a photoresist is known. This method is a method in which a substrate coated with a photoresist polymer or applied with a photoresist on a dry film is UV-exposed through an arbitrary photomask to form a pattern such as a lattice. It is useful for forming an electromagnetic wave shield that requires high performance.
However, in recent years, with the progress of development of micromachines and further miniaturization of VLSI, these wiring structures have been required to be fine in nano units, and conventional metal etching is becoming finer. There is a limit, and there is a concern about disconnection during processing of the thin wire portion.

As a technique to deal with the problem of pattern miniaturization and disconnection, a conductive pattern material is formed by forming a hydrophilic polymer pattern on the support surface and forming a conductive material layer on the hydrophilic pattern. Is known (see, for example, Patent Document 1). Such a conductive material layer is composed of conductive particles that are ionically adsorbed and immobilized on the graft polymer bonded to the surface of the substrate, and this conductive pattern material has a high resolution. Thus, a conductive pattern without disconnection can be obtained. However, there is a concern that the conductive particles fixed by ionic bonds, such as the conductive pattern material, may be detached from the graft polymer when touching an electrolyte solution such as saline.
For this reason, in addition to being able to form a conductive pattern with high resolution and no disconnection, further improvement of the durability of the conductive pattern is desired at present.
JP 2003-114525 A

An object of the present invention is to solve various problems in the prior art and achieve the following objects.
That is, an object of the present invention is to provide a method for producing a conductive pattern material having a conductive pattern with high resolution, no disconnection, and excellent durability.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by introducing a crosslinked structure into a conductive particle adsorption layer containing a graft polymer to which conductive particles have been adsorbed, and have arrived at the present invention. It came to do.

That is, a functional group capable of interacting with the conductive particles (hereinafter referred to as “interactive group” as appropriate) and a crosslinkable functional group (hereinafter referred to as “crosslinkable group” as appropriate) on the substrate. A step of directly bonding the graft polymer having a pattern,
A step of adsorbing the conductive particles to a functional group capable of interacting with the conductive particles of the graft polymer to form a conductive particle adsorption layer;
Forming a crosslinked structure in the conductive particle adsorption layer by applying energy to the conductive particle adsorption layer;
It is a manufacturing method of the electroconductive film characterized by having.

As described above, in the present invention, the graft polymer is directly bonded to the base material in a pattern, and the conductive particles are adsorbed on the interactive group of the graft polymer to provide the conductive particle adsorption layer. A crosslinkable group present in the polymer is reacted to form a crosslinked structure in the conductive particle adsorption layer.
Although the operation of the present invention is not clear, it is presumed as follows.
In the present invention, by forming a crosslinked structure in the conductive particle adsorption layer, the conductive particles adsorbed on the interactive group of the graft polymer are further included in the crosslinked structure and physically immobilized. The Rukoto. As a result, the conductive particle adsorption layer according to the present invention is caused by the presence of the crosslinked structure in the conductive particle adsorption layer in addition to the retention of the conductive particles due to the presence of the interactive group of the graft polymer. It is considered that the retention of conductive particles is remarkably improved by immobilization.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the electroconductive pattern material provided with the electroconductive pattern which is high resolution, has no disconnection, and is excellent in durability can be provided.

Hereinafter, the present invention will be described in detail.
A step of directly bonding a graft polymer having a functional group capable of interacting with conductive particles (interactive group) and a crosslinkable group on a substrate in a pattern (hereinafter referred to as “graft polymer pattern forming step” as appropriate). )When,
A step of adsorbing conductive particles to a functional group capable of interacting with the conductive particles of the graft polymer to form a conductive particle adsorption layer (hereinafter referred to as “conductive particle adsorption layer forming step” as appropriate); ,
A step of forming a crosslinked structure in the conductive particle adsorption layer by applying energy to the conductive particle adsorption layer (hereinafter, appropriately referred to as a “crosslinked structure formation step”);
It is characterized by having.
Hereafter, each process in this invention is demonstrated sequentially.

<Graft polymer pattern formation process>
In the present invention, first, a graft polymer pattern is formed on a substrate in a graft polymer pattern forming step.

(Surface graft polymerization method)
The graft polymer in the present invention is preferably formed by a surface graft polymerization method.
In general, the surface graft polymerization method gives an active species on a polymer compound chain forming a solid surface, and further polymerizes another monomer starting from this active species to synthesize a graft (grafting) polymer. Is the method.

Any of the known methods described in the literature can be used as the surface graft polymerization method for realizing the present invention. For example, New Polymer Experimental Science 10, edited by Polymer Society of Japan, 1994, published by Kyoritsu Shuppan Co., Ltd., p135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods. In addition, the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, 1999.2, p203, p695 describes radiation-induced graft polymerization methods such as γ rays and electron beams.
As a specific method of the photograft polymerization method, methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used.

In the plasma irradiation graft polymerization method and the radiation irradiation graft polymerization method, the literatures described above and Y.C. Ikada et al, Macromolecules vol. 19, page 1804 (1986). Specifically, a graft polymer can be obtained by treating a polymer surface such as PET with plasma or electron beam, generating radicals on the surface, and then reacting the active surface with a nomer.
In addition to the above-mentioned documents, the photograft polymerization method can be applied to the surface of a film substrate as described in JP-A-53-17407 (Kansai Paint) or JP-A-2000-212313 (Dainippon Ink). The grafted polymer can be obtained by applying a photopolymerizable composition to the substrate, and then contacting the radically polymerized compound and irradiating it with light.

  As other means for bonding the graft polymer to the base material, in addition to these, a reactive functional group such as trialkoxysilyl group, isocyanate group, amino group, hydroxyl group, and carboxyl group is added to the terminal of the polymer compound chain, It is also possible to use a method in which a polymer compound chain is introduced into the substrate surface by a coupling reaction between this and a substrate surface functional group.

A specific method in the case of using the surface graft polymerization method in the graft polymer pattern forming step in the present invention will be described.
In the present invention, an exposed portion of the substrate surface is obtained by bringing a polymerizable compound having an interactive group and a polymerizable compound having a crosslinkable group shown below into contact with the substrate surface and applying energy in a pattern. An active site is generated, and the active site reacts with the polymerizable group of the polymerizable compound to cause a surface graft polymerization reaction.
The contact of the polymerizable compound with the substrate surface may be carried out by immersing the substrate in a liquid composition containing the polymerizable compound. However, from the viewpoint of handleability and production efficiency, the polymerization may be performed. It is preferable to carry out by applying a liquid composition containing a functional compound to the substrate surface.

(Generation of graft polymer)
In the present invention, the graft polymer directly bonded to the substrate is a graft polymer having an interactive group and a crosslinkable group, and the polymer structure has an interactive group and a crosslinkable group. Thus, both functions of adsorption of conductive particles and formation of a crosslinked structure can be exhibited.

The graft polymer in the present invention is formed by copolymerization of a polymerizable compound having an interactive group and a polymerizable compound having a crosslinkable group. By using the surface graft polymerization method described above, a base material is obtained. On top of this, the graft polymer which is this copolymer can be directly bonded.
The polymerizable compound having an interactive group and the polymerizable compound having a crosslinkable group may be any of a monomer, a macromer, and a polymer having a polymerizable group. It is particularly preferred.

As the monomer having an interactive group and the monomer having a crosslinkable group used for the formation of the graft polymer, one type each may be used, or a plurality of types of monomers may be used in combination.
In the formation of the graft polymer in the present invention, it is necessary to use at least one monomer having an interactive group and one monomer having a crosslinkable group. You may use other copolymerization monomers other than.

The content ratio of the monomer component having an interactive group and the monomer component having a crosslinkable group in the graft polymer is 30:70 to 30 in terms of molar ratio from the viewpoint of coexistence of adsorption of conductive particles and formation of a crosslinked structure. 99: 1 is preferable, 50:50 to 95: 5 is more preferable, and 60:40 to 90:10 is still more preferable.
Details of matters relating to adsorption of conductive particles and matters relating to formation of a crosslinked structure will be described in detail in the description of “conductive particle adsorption layer forming step” and “crosslinked structure forming step” described later.

  Hereinafter, the monomer having an interactive group and the monomer having a crosslinkable group, which can be used for forming the graft polymer in the present invention, will be described in detail.

-Monomer having an interactive group-
The interactive group possessed by the graft polymer is a functional group having interactive properties according to the conductive particles adsorbed on the graft polymer.
In the present invention, the interactive group is a functional group capable of adsorbing conductive particles, but may function as a functional group having a structure used for a crosslinking reaction when the conductive particles are not adsorbed. .

  The interactive group in the present invention is preferably a polar group, and more preferably an ionic group. Accordingly, a monomer having an ionic group (ionic monomer) is preferably used as the monomer having an interactive group in the present invention.

  As the ionic monomer, a monomer having a positive charge such as ammonium or phosphonium, or a negative charge such as a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group can be dissociated into a negative charge. And monomers having an acidic group.

  As described above, the ionic monomer that can form an ionic group that can be suitably used in the present invention is a monomer having a positive charge such as ammonium or phosphonium, a sulfonic acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid. And monomers having a negative charge such as a group or an acidic group that can be dissociated into a negative charge.

  Specific examples of the ionic monomer particularly useful 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 its alkali metal salts and amine salts, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or their salts, 2-dimethylaminoethyl (medium) ) 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.

Moreover, the monomer which has a nonionic polar group as shown below as an interactive group can also be used.
That is, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) ) Acrylate is useful.

  As the monomer having an interactive group in the present invention, a monomer having an anionic functional group such as acrylic acid (anionic monomer) is particularly preferable.

-Monomer having a crosslinkable group-
The crosslinkable group that the graft polymer has is a reactive group that reacts with an interactive group or another functional group that the graft polymer has to form a covalent bond, such as a hydroxyl group, a methylol group, a glycidyl group, an isocyanate group, Examples include functional groups such as amino groups.

In the present invention, a monomer having a crosslinkable group (that is, a reactive monomer) that can be used can be appropriately selected from known ones.
Specific examples of the monomer having a crosslinkable group include, for example, 2-hydroxyethyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxybutyl methacrylate, Those having a hydroxyl group such as 2-hydroxybutyl methacrylate and 4-hydroxybutyl methacrylate; Those having a methylol group such as N-methylolacrylamide, N-methylolmethacrylamide, and methylol stearamide; Glycidyl groups such as glycidyl acrylate and glycidyl methacrylate Having an isocyanate group such as 2-isocyanate ethyl methacrylate (for example, trade name: Karenz MOI, Showa Denko) Shall; 2-aminoethyl acrylate, such as those having amino group such as 2-aminoethyl methacrylate are mentioned.

The solvent used in the liquid composition containing such a monomer having an interactive group and a monomer having a crosslinkable group is not particularly limited as long as these monomers as main components can be dissolved, but water, An aqueous solvent such as a water-soluble solvent is preferable, and a mixture thereof or one obtained by further adding a surfactant to the solvent is preferable.
The water-soluble solvent refers to a solvent that is 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.
The coating amount when this liquid composition is applied to the substrate surface to form a liquid composition coating layer is 0 in terms of solid content from the viewpoint of obtaining sufficient adsorbability of conductive particles and obtaining a uniform coating film. .1 to 10 g / m ² is preferable, and 0.5 to 5 g / m ² is particularly preferable.

  Further, a surfactant can be added to the liquid composition as necessary. This surfactant only needs to be soluble in the solvent in the liquid composition. Examples of such surfactants include anionic surfactants such as sodium n-dodecylbenzenesulfonate, n- Cationic surfactants such as dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products such as Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate (commercially available products such as , Trade name “Tween 20”, etc.), and nonionic surfactants such as polyoxyethylene lauryl ether.

(Pattern-shaped energy application)
When the graft polymer pattern is formed in this step, as described above, the monomer having an interactive group and the monomer having a crosslinkable group are brought into contact with the surface of the substrate, and energy is applied in a pattern. The energy applying means used here is not particularly limited as long as it can generate active sites on the surface of the substrate, but from the viewpoint of cost and simplicity of the apparatus, a method of irradiating actinic rays is used. It is preferable.
As the actinic ray, various rays such as infrared rays, visible rays, ultraviolet rays, and radiations are used. Among these, ultraviolet rays are preferably used because they are suitable for high-definition pattern exposure. Moreover, as a radiation, an electron beam, an X-ray, an ion beam, far infrared rays, etc. are used. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) can also be used. Suitable examples of these light sources include mercury lamps, metal halide lamps, xenon lamps, chemical lamps, and carbon arc lamps.
When actinic light irradiation is used as pattern-like energy application, both scanning exposure based on digital data and pattern exposure using a lith film or mask film can be used.

(Base material)
The substrate used in the present invention is a dimensionally stable plate-like material, and any material can be used as long as necessary flexibility, strength, durability, etc. are satisfied, and it is appropriately selected according to the purpose of use. Is done.
When selecting a transparent substrate that requires light transmission, for example, glass, plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate) Polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.).
In addition, as the base material of conductive pattern material that does not require transparency, polyimide resin, bismaleimide resin, polyphenylene oxide resin, epoxy resin, liquid crystal polymer, polytetrafluoroethylene resin, etc., silicone substrate Paper, paper laminated with plastic, metal plate (for example, aluminum, zinc, copper, etc.), paper or plastic film laminated with metal such as those mentioned above, and the like.

In the present invention, the substrate is appropriately selected according to the use of the conductive pattern material and the relationship with the adsorbed conductive particles, but from the viewpoint of processability and transparency, the surface made of a polymer resin is used. The base material which has is preferable, and specifically, any of a resin film, a transparent inorganic base material such as glass whose surface is coated with a resin, and a composite material whose surface layer is a resin layer are suitable.
Representative examples of the substrate having a resin coated surface include a laminate having a resin film attached to the surface, a primer-treated substrate, and a hard-coated substrate. Typical examples of the composite material in which the surface layer is a resin layer include a resin sealing material in which an adhesive layer is provided on the back surface, and a laminated glass that is a laminate of glass and resin.

Further, the base material may be subjected to a surface roughening treatment according to the purpose of use.
For example, in order to increase the adsorption amount per unit area of conductive particles in the conductive pattern, the surface of the substrate is roughened in advance for the purpose of increasing the surface area and introducing more ionic groups. Is possible.
As a method for roughening the substrate, a known method suitable for the material of the substrate can be selected. Specifically, for example, when the substrate is a resin film, glow discharge treatment, sputtering, sandblast polishing method, buff polishing method, particle adhesion method, particle coating method and the like can be mentioned. Further, when the base material is an inorganic material such as a glass plate, a mechanical roughening method can be applied. As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used.

-Base material surface or intermediate layer-
As described above, the substrate in the present invention has a surface on which the graft polymer can be directly bonded chemically. In the present invention, the surface of the substrate itself may have such characteristics, and an intermediate layer having such characteristics may be provided on the surface of the substrate.

  As the intermediate layer, in particular, when a graft polymer is synthesized by a photograft polymerization method, a plasma irradiation graft polymerization method, or a radiation irradiation graft polymerization method, a layer having an organic surface is preferable. Preferably there is. Organic polymers include epoxy resins, acrylic resins, urethane resins, phenol resins, styrene resins, vinyl resins, polyester resins, polyamide resins, melamine resins, formalin resins and other synthetic resins, gelatin, casein, and cellulose. Any natural resin such as starch can be used. In the photograft polymerization method, plasma irradiation graft polymerization method, radiation irradiation graft polymerization method, etc., since the start of graft polymerization proceeds from the extraction of hydrogen of the organic polymer, polymers that are easy to extract hydrogen, especially acrylic resin, urethane resin, styrene It is particularly preferable from the viewpoint of production suitability to use a resin, vinyl resin, polyester resin, polyamide resin, epoxy resin or the like.

-Layer that exhibits polymerization initiation ability-
In the present invention, as a compound that exhibits polymerization initiating ability by applying energy to the substrate surface, a polymerizable compound and a polymerization initiator are added, and an intermediate layer or a layer that exhibits polymerization initiating ability as the substrate surface. It is preferable from the viewpoint of efficiently generating active sites during graft polymerization.
The layer that expresses the polymerization initiating ability (hereinafter referred to as a polymerizable layer as appropriate) is prepared by dissolving necessary components in a solvent capable of dissolving them, and providing them on the surface of the substrate by a method such as coating. It can be hardened and formed by irradiation.

(A) Polymerizable compound The polymerizable compound used in the polymerizable layer has good adhesion to the substrate, and has a monomer having an interactive group and a crosslinkable group by applying energy such as irradiation with actinic rays. Although there will be no restriction | limiting in particular if the monomer which has can be added, Especially, the hydrophobic polymer which has a polymeric group in a molecule | numerator is preferable.
Specific examples of such hydrophobic polymers include diene homopolymers such as polybutadiene, polyisoprene, and polypentadiene, and allyl groups such as allyl (meth) acrylates and 2-allyloxyethyl methacrylates. Monomer homopolymer;
Furthermore, binary or multicomponent with styrene, (meth) acrylic acid ester, (meth) acrylonitrile, etc. containing diene monomer such as polybutadiene, polyisoprene, polypentadiene or allyl group-containing monomer as a constituent unit. Copolymer;
And linear polymers or three-dimensional polymers having a carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, and high-density polyethylene.
In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.
The content of the polymerizable compound is preferably in the range of 0 to 100% by mass and particularly preferably in the range of 10 to 80% by mass in terms of solid content in the polymerizable layer.

(B) Polymerization initiator The polymerizable layer in the present invention preferably contains a polymerization initiator for expressing the polymerization initiating ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, or the like that can exhibit polymerization initiating ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Can be selected and used as appropriate. Among these, use of photopolymerization having a higher reaction rate (polymerization rate) than thermal polymerization is preferable from the viewpoint of production suitability, and therefore, a photopolymerization initiator is preferably used.
The photopolymerization initiator is active with respect to irradiated actinic rays, and can polymerize a polymerizable compound contained in the polymerizable layer, a monomer having an interactive group, and a monomer having a crosslinkable group. If possible, there is no particular limitation, and for example, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator and the like can be used.

Specific examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Acetophenones such as: benzophenone (4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, ketones; benzoin, benzoin methyl ether, benzoin isopropyl Examples thereof include benzoin ethers such as ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone, and the like.
The content of the polymerization initiator in the polymerizable layer is preferably in the range of 0.1 to 70% by mass and particularly preferably in the range of 1 to 40% by mass in terms of solid content.

The solvent used when applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The concentration of the solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount in the case of forming the polymerizable layer on the substrate is, in terms of sufficient polymerization initiating ability and maintaining the film property to prevent film peeling, and the weight after drying is 0.00. 1-20 g / m < ² > is preferable and 1-15 g / m < ² > is more preferable.

As described above, the polymerizable layer forming composition is disposed on the surface of the substrate by coating or the like, and the solvent is removed to form a polymerizable layer to form a polymerizable layer. It is preferable that the film is hardened by light irradiation. In particular, if the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is cured to some extent in advance, so that the polymerizable layer falls off after the graft polymer is formed on the substrate. Such a situation can be effectively suppressed. Here, the reason why light irradiation is used for pre-curing is the same as described in the section of the photopolymerization initiator.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried. However, from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, and the drying temperature is 40 to 80 ° C. It is more preferable to select heating conditions within a drying time of 10 minutes.

  Light irradiation performed as desired after heat drying includes, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp as a light source. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used. From the viewpoint of not inhibiting the subsequent formation of the graft polymer and the formation of the bond between the active site of the polymerizable layer and the graft chain, which is performed by applying energy, the polymerizable compound present in the polymerizable layer is partially Even if radical polymerization is performed, it is preferable to irradiate with light to such an extent that radical polymerization does not occur completely. The light irradiation time varies depending on the intensity of the light source, but is generally preferably within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent washing is 10% or more and the initiator remaining rate after pre-curing is 1% or more.

In the present invention, as one of preferred embodiments for generating a graft polymer on a substrate, a compound having a polymerization initiating ability is bound to the surface of the substrate, and the graft polymer is started from the polymerization initiation site of the compound. The mode which produces | generates is mentioned.
Examples of the compound having a polymerization initiating ability applicable to the above embodiment include a compound having a polymerization initiation site (Q) capable of initiating radical polymerization by photocleavage and a substrate binding site (Y) (hereinafter referred to as “light” as appropriate). Cleaving compound (QY) ").

Hereinafter, a method for bonding the photocleavable compound (QY) to the substrate surface will be described.
In order to bond the photocleavable compound (QY) to the substrate surface, the photocleavable compound (QY) is imparted on the substrate, brought into contact with the substrate surface, and a functional group present on the substrate surface ( Z) and the base material binding site (Q) may be combined to introduce the photocleavable compound (QY) onto the base material surface.

  Specific examples of the functional group (Z) present on the substrate surface include a hydroxyl group, a carboxyl group, and an amino group. These functional groups may be originally present on the surface of the base material due to the material of the base material in the silicon substrate or glass substrate, and may be present on the surface by subjecting the base material surface to a surface treatment such as corona treatment. It may be.

A polymerization initiation site capable of initiating radical polymerization 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 a starting point for graft polymerization in the graft polymer pattern forming step, the cleavage reaction occurs when the single bond that can be cleaved by light is cleaved. 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, 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.
Therefore, when a graft polymer is produced using a substrate having a photocleavable compound (QY) introduced on the surface, exposure at a wavelength that can cleave the polymerization initiation site (Y) as an energy imparting means. Must be used.

  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 substrate surface. Specific examples of the reactive group are shown below. Such groups are mentioned.

  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. However, it is not limited to these.

As a specific method for bonding the photocleavable compound (QY) to the functional group (Z) present on the substrate surface, the photocleavable compound (QY) is mixed with an appropriate solvent such as toluene, hexane or acetone. Or a method of applying the solution or dispersion to the surface of the substrate or a method of immersing the substrate in the solution or dispersion. By these methods, the substrate surface into which the photocleavable compound (QY) has been introduced is 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.

In the case of using the base material with the photocleavable compound (QY) introduced on the surface, the monomer having an interactive group and the monomer having a crosslinkable group are brought into contact with the surface. A method of forming a graft polymer pattern by cleaving the polymerization initiation site (Y) of the exposed portion by pattern exposure and generating a graft polymer starting from the site is used.
Moreover, a graft polymer pattern can also be formed with the following method.
First, pattern exposure is performed in advance along a region where a graft polymer is not desired to be formed on the surface of the substrate into which the photocleavable compound (QY) has been introduced, and the compound (QY) bonded to the substrate surface. ) Is photocleavaged to deactivate the polymerization initiating ability, thereby forming a polymerization initiation capable region and a polymerization initiating ability deactivating region on the surface of the substrate. Then, after bringing the monomer having an interactive group and the monomer having a crosslinkable group into contact with the substrate surface on which the polymerization startable region and the polymerization initiating ability deactivation region are formed, the entire surface is exposed to polymerize In this method, a graft polymer is formed only in the startable region, and as a result, a graft polymer pattern is formed.

  As described above, a graft polymer pattern in which a graft polymer is bonded in a pattern is formed on the substrate, and then a conductive particle adsorption layer forming step is performed.

<Conductive particle adsorption layer forming step>
In the conductive particle adsorption layer forming step, the conductive particles are adsorbed on the interactive group of the graft polymer generated in a pattern to form a patterned conductive particle adsorption layer.
The conductive particles adsorbed on the interactive group of the graft polymer are described by taking an ionic group as the interactive group, and are arranged regularly in a substantially monolayer state depending on the presence state of the ionic group, One nanoscale fine particle is adsorbed to each ionic group of the long graft polymer chain, and as a result, it is arranged in a multilayer state.

Next, the conductive particles that can be used in the present invention will be specifically described.
As the conductive particles, it is preferable to use at least one kind of fine particles selected from conductive metal particles and metal oxide particles, metal oxide particles and metal compound fine particles having semiconductor characteristics, and conductive resin fine particles. .
As the conductive metal particles and the metal oxide particles, a conductive metal or metal oxide powder having a specific resistance value of 1 × 10 ³ Ω · cm or less can be widely used. Specifically, For example, silver (Ag), gold (Au), nickel (Ni), copper (Cu), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), iron (Fe), platinum (Pt ), Iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Ru), tungsten (W), molybdenum (Mo), etc. and their alloys, as well as tin oxide (SnO ₂₎ ), Indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), ruthenium oxide (RuO ₂ ), and the like can be used.
In addition, metal oxide particles and metal compound particles having the above characteristics as a semiconductor may be used. For example, In ₂ O ₃ , SnO ₂ , ZnO, Cdo, TiO ₂ , CdIn ₂ O ₄ , Cd ₂ SnO ₂ , Oxide semiconductor particles such as Zn ₂ SnO ₄ and In ₂ O ₃ —ZnO, particles using a material doped with impurities suitable for these, and spinel compound particles such as MgInO and CaGaO, TiN, ZrN , Conductive nitride particles such as HfN, and conductive boride particles such as LaB.
These electroconductive particles may be used independently and may use 2 or more types together. In order to obtain desired conductivity, a plurality of materials can be mixed and used in advance.
In addition, since electroconductive particle adsorb | sucks ionically with respect to an interactive group as a preferable aspect, a particle size and adsorption amount are restrict | limited by the surface charge of electroconductive particle, and the number of ionic groups. Needless to say.

  The particle size of the conductive particles can be selected according to the purpose and application, but is generally preferably in the range of 0.1 nm to 1 μm from the viewpoint of conductivity and adsorbability. The range of 1 nm to 300 nm is more preferable, and the range of 5 nm to 100 nm is particularly preferable.

-Relationship between interactive groups (ionic groups) of graft polymer and conductive particles-
When the graft polymer generated on the substrate has an anionic interactive group (ionic group) such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group, the interactive group is negative. Since it has a charge, a conductive particle adsorbing layer is formed by adsorbing cationic conductive particles having a positive charge here.

  Examples of such cationic conductive particles include positively charged metal (oxide) fine particles. The 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 graft polymer produced on the substrate has an interactive group (ionic group) such as an ammonium group described in JP-A-10-296895, the interactive group is Since it has a positive charge, a conductive particle adsorption layer is formed by adsorbing conductive particles having a negative charge here.
Examples of negatively charged conductive particles include gold or silver particles obtained by citric acid reduction.

As a method of adsorbing the conductive particles to the interactive group (ionic group) of the graft polymer, a method of applying a liquid in which the conductive particles are dissolved or dispersed to the substrate surface on which the graft polymer pattern is formed, And the method of immersing the base material in which the graft polymer pattern was formed in the liquid which melt | dissolved or disperse | distributed electroconductive particle is mentioned.
In either case of application or immersion, an excessive amount of conductive particles is supplied, and sufficient ionic bond is introduced between the graft polymer interacting groups (ionic groups). The contact time between the dispersion and the graft polymer production surface is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.
In addition, it is preferable that the conductive particles are bonded in the maximum amount that can be adsorbed to the hydrophilic group of the graft polymer. From the viewpoint of ensuring conductivity, the dispersion concentration of the dispersion containing the conductive particles is set to 0. About 001-20 mass% is preferable.

In this manner, the conductive particles are adsorbed on the interactive group of the graft polymer directly bonded to the base material, so that a patterned conductive particle adsorption layer can be obtained.
The film thickness of the conductive particle adsorbing layer can be selected depending on the purpose, but generally from the viewpoint of scratch resistance (film strength), transparency, etc., the range of 0.001 μm to 10 μm is preferable, and 0.01 μm to The range of 5 μm is more preferable, and the range of 0.1 μm to 2 μm is most preferable.

<Crosslinked structure forming step>
In the crosslinked structure forming step, energy is applied to the conductive particle adsorption layer formed by the conductive particle adsorption step, thereby forming a crosslinked structure in the conductive particle adsorption layer.

  In the formation of the crosslinked structure, (1) an interactive group to which conductive particles are not adsorbed may be used for forming the crosslinked structure, and (2) the interactive group adsorbs conductive particles. It may be an embodiment that is used only for forming a cross-linked structure.

Examples of the graft polymer in the formation of the crosslinked structure (1) and (2) are as follows.
Examples of the case (1) include a case where the graft polymer is a binary polymer of a monomer having a carboxyl group and a monomer having a glycidyl group.
In the case of the above (2), for example, when the graft polymer is a terpolymer of a monomer having a carboxyl group, a monomer having a hydroxyl group, and a monomer having an isocyanate group, or the graft polymer is a carboxyl group And a case where the monomer is a binary polymer of N-methylolacrylamide or the like which can react with itself to form a crosslinked structure.

The cross-linking reaction is caused by applying energy to the conductive particle adsorption layer. Examples of the energy application include heating, light irradiation, ultrasonic irradiation, and electron beam irradiation.
In the present invention, it is preferable that the crosslinked structure is formed by heating. As a specific example, there can be mentioned a reaction between a carboxyl group which is an interactive group of the graft polymer and a glycidyl group which is a crosslinkable group.

In the case where the energy application is performed by heating, as the heating means, for example, an oven or a hot plate using a heater, heating by photothermal conversion using infrared rays or visible light, or the like can be used.
Moreover, although heat processing changes with kinds of graft polymer formed, it is performed by heating at 50 to 300 degreeC for about 0.1 second-60 minutes.
In the case where the energy application is performed by light irradiation, as the light irradiation means, for example, a light source in the ultraviolet to visible range such as various mercury lamps from a low pressure to a high pressure, a metal halide lamp, and a xenon lamp can be used.

In this way, a crosslinked structure is formed in the conductive particle adsorption layer. The crosslinking rate in this crosslinked structure can be estimated by the mass increase rate after the conductive particle adsorption layer having the crosslinked structure formed is immersed in a solvent for a certain time. The solvent used here is selected from solvents having the highest affinity for the conductive particle adsorption layer in which a crosslinked structure is formed, and the graft polymer constituting the conductive particle adsorption layer is an ionic monomer or In the case of being produced from a monomer having a polar group, water, N, N-dimethylacetamide, or the like can be selected.
The mass increase rate of the conductive particle adsorption layer in which the crosslinked structure is formed is preferably 30% or less, more preferably 10% or less, and particularly preferably 5% or less.
In addition, when the base material provided with such a conductive particle adsorption layer has no affinity for the solvent used when estimating the cross-linking rate, the cross-linked structure is not affected even if the base material is immersed in the solvent. The mass increase rate of the formed conductive particle adsorption layer can be calculated.

  A conductive pattern material can be manufactured by each process which concerns on the manufacturing method of this invention demonstrated above.

  In the conductive pattern material obtained by the present invention, the conductive particles are electrostatically and uniformly adsorbed uniformly on the interactive group of the graft polymer by bonding the graft polymer directly on the substrate. It has a conductive particle adsorption layer. Moreover, in this invention, since the layer which the electroconductive particle adsorb | sucked in the single layer state or the multilayer state was formed in the interactive group which a graft polymer has, high electroconductivity can be expressed. Furthermore, since the cross-linked structure is formed in the conductive particle adsorption layer, the conductive particles are firmly fixed in the conductive particle adsorption layer, resulting in the environment where the conductive film is used. Thus, no detachment of the conductive particles occurs, there is no problem of disconnection, and the conductive durability is excellent.

  Such conductive pattern materials can be used for various circuit formation applications, and in particular, since a fine conductive pattern can be formed, a wide range of applications including circuit formation such as micromachines and VLSI is expected. Is done. In addition to this, various uses such as fine electrical wiring, high-density magnetic disk, magnetic head, magnetic tape, magnetic sheet, and magnetic disk can be expected, and its application range is wide.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[Example 1]
[1. Graft polymer pattern formation process)
Using PET (188 μm, manufactured by Toray Industries, Inc.) as a base material, the following photopolymerizable composition is applied to the surface using a rod bar 18 and dried at 80 ° C. for 2 minutes to form an intermediate layer having a thickness of 6 μm. did.

<Photopolymerizable composition>
・ Allyl methacrylate / methacrylic acid copolymer 2g
(Copolymerization molar ratio 80/20, average molecular weight 100,000)
・ Ethylene oxide modified bisphenol A diacrylate 4g
・ 1.6g of 1-hydroxycyclohexyl phenyl ketone
・ 16 g of 1-methoxy-2-propanol

-Formation of graft polymer-
Next, 5 ml of a 5% by weight monomer aqueous solution of acrylic acid / glycidyl methacrylate (molar ratio: 80/20) is dropped on the intermediate layer, and a quartz plate is placed thereon to uniformly distribute the monomer aqueous solution to the intermediate layer. And sandwiched between quartz plates. The pattern mask (NC-1, manufactured by Toppan Printing Co., Ltd.) is clipped onto the quartz plate, and then, from above the pattern mask, using an exposure machine (UVX-02516S1LP01, manufactured by USHIO INC.). Exposed for 5 minutes. As described above, a base material in which a graft polymer composed of a copolymer of acrylic acid and glycidyl methacrylate was bonded to the surface of the base material in a pattern was obtained.
The substrate on which this graft polymer pattern was obtained is referred to as substrate A.

[2. Conductive particle adsorption layer formation process]
The substrate A was immersed in a positively charged Ag particle dispersion obtained as follows, and then the surface was washed thoroughly with running water to remove excess particle dispersion, and the conductive particles were An adsorbed conductive particle adsorption layer was obtained.

(Preparation of Ag particle dispersion)
Add 3 g of bis (1,1-trimethylammonium decanoylaminoethyl) disulfide to 50 ml of ethanol solution (5 mmol / l) of silver perchlorate, and add 30 ml of sodium borohydride solution (0.4 mol / l) with vigorous stirring. The ions were slowly dropped to reduce the ions, and a dispersion of silver particles coated with quaternary ammonium was obtained. When the size of the silver particles was measured with an electron microscope, the average particle size was 5 nm.

[3. (Crosslinked structure forming step)
The substrate A on which the conductive particle adsorption layer is formed is heated at 140 ° C. for 5 minutes using a hot plate (model: T2B, manufactured by Bamstead) to crosslink the carboxyl group and glycidyl group of the graft polymer. Thus, a crosslinked structure was formed in the conductive particle adsorption layer.
As described above, a conductive pattern material A of Example 1 was obtained.

[Example 2]
[1. Graft polymer pattern formation process)
(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)
A glass substrate (manufactured by Nippon Sheet Glass Co., Ltd.) as a base material 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 base material in which the photocleavable compound was introduced on the surface was obtained.

(Deactivation of polymerization initiation ability)
A pattern mask (NC-1, manufactured by Toppan Printing Co., Ltd.) is clipped to one side of the substrate into which the photocleavable compound has been introduced, and the pattern is exposed for 1 minute with an exposure machine (UVX-02516S1LP01, manufactured by USHIO INC.). Exposure was performed. This obtained the base material in which the polymerization start possible area | region and the polymerization initiating ability deactivation area | region were formed.

-Formation of graft polymer-
Next, 5 ml of a 5 mass% monomer aqueous solution of acrylic acid / glycidyl methacrylate (molar ratio: 80/20) was dropped on the surface of the base material on which the polymerization startable region and the polymerization initiating ability deactivation region were formed. A quartz plate was placed on top, and the monomer aqueous solution was uniformly sandwiched between the intermediate layer and the quartz plate. From the quartz plate, the entire surface was exposed for 5 minutes using an exposure machine (UVX-02516S1LP01, manufactured by USHIO INC.). As described above, a base material in which a graft polymer composed of a copolymer of acrylic acid and glycidyl methacrylate was bonded to the surface of the base material in a pattern was obtained.
The base material from which this graft polymer pattern was obtained is referred to as base material B.

[2. 2. a conductive particle adsorption layer forming step; (Crosslinked structure forming step)
For this base material B, the same as in Example 1, 2. 2. a conductive particle adsorption layer forming step; A cross-linked structure forming step was performed to obtain a conductive pattern material B of Example 2.

[Comparative Examples 1 and 2]
In the graft polymer formation in the kraft polymer production step of Examples 1 and 2, instead of producing a graft polymer consisting of acrylic acid and glycidyl methacrylate (80/20 molar ratio), a graft polymer consisting only of acrylic acid was produced, And except having not performed the crosslinked structure formation process, it carried out similarly to Examples 1 and 2, and obtained electroconductive pattern material C and D of comparative examples 1 and 2, respectively.

<Evaluation>
(Confirmation of conductive pattern)
When the conductive particle adsorption layer (conductive pattern) of the conductive pattern materials A to D produced in the examples and comparative examples is confirmed with a transmission electron microscope (JEOL JEM-200CX) at a magnification of 100,000 times. In either case, it was confirmed that fine wiring having a line width of 8 μm / space width of 8 μm was formed.

(Evaluation of surface conductivity)
The surface conductivity of the conductive particle adsorbing layers (conductive patterns) of the conductive pattern materials A to D produced in the examples and comparative examples was measured using four probes using LORESTA-FP (manufactured by Mitsubishi Chemical Corporation). Measured by the method. The measurement results are shown in Table 1 below.

(Durability evaluation)
The conductive pattern materials A to D produced in Examples and Comparative Examples were each immersed in saturated saline for 10 minutes, and the surface conductivity before and after immersion was compared to evaluate the retention durability of the conductive particles. . Here, the measurement method of surface conductivity is the same as the measurement method of surface conductivity in evaluation of conductivity. The surface conductivity before immersion is the result of the evaluation of the surface conductivity. The measurement results are shown in Table 1 below.

From the above evaluation results, the conductive pattern materials A and B of Examples 1 and 2 in which a crosslinked structure was formed in the conductive particle adsorption layer were maintained with high surface conductivity before and after immersion in saturated saline solution. It turns out that it is excellent in durability.
On the other hand, the conductive pattern material C of Comparative Examples 1 and 2, in which a graft polymer composed only of acrylic acid was generated to form a conductive particle adsorption layer and a crosslinked structure was not formed in the conductive particle adsorption layer, D shows the same surface conductivity as that of the example before immersion in the saturated saline solution, but after the saturated saline solution, the surface conductivity is remarkably lowered, and the detachment of the conductive particles occurs. Presumed to be.

Claims (1)

Directly bonding a graft polymer having a functional group capable of interacting with conductive particles and a crosslinkable functional group in a pattern on a substrate;
A step of adsorbing the conductive particles to a functional group capable of interacting with the conductive particles of the graft polymer to form a conductive particle adsorption layer;
Forming a crosslinked structure in the conductive particle adsorption layer by applying energy to the conductive particle adsorption layer;
The manufacturing method of the conductive pattern material characterized by having.