JP2005272961A - Conductive pattern material, metal particulate pattern material, and method for forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive pattern material which is high in conductivity, high in fineness and wide in an application range, and a metal particulate pattern material which is dispersed with metal particulates in high density and has a metal particulate adsorption region of excellent durability, and further, a pattern forming method capable of manufacturing these materials by a simple process with high productivity. <P>SOLUTION: A surface graft material having a graft polymer chain directly bonded by covalent bonding at one terminal is exposed through an optically cleavable area on the surface of a base material and the optically cleavable area is cloven in the exposed region. The region where the graft polymer chain exists/the region where the graft polymer chain does not exist are formed by removing the graft polymer chains and thereafter metal ions or metal salt is imparted to the region where the graft polymer chain exists to reduce the metal ions or the metal ions in the metal salt and to precipitate the metal. The thin metal film is thus formed to provide the conductive pattern material or the metal particulate adsorption region is formed to provide the metal particulate pattern material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a conductive pattern material, a metal fine particle pattern material, and a pattern forming method thereof, and more specifically, an electrical wiring formed by forming a metal thin film such as silver or copper or a metal fine particle region on a base material. The present invention relates to a conductive pattern material, a metal fine particle pattern material, and a pattern forming method thereof that are useful for materials, electromagnetic wave prevention films, magnetic films and the like, have high density, and are excellent in durability and productivity.

Conventionally, various conductive pattern materials have been used for forming a wiring board. 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, an etching process is performed to form a desired pattern, and at least four processes are required. When wet etching is performed, a waste liquid processing process is also required. It must be taken (see, for example, Patent Document 1).
As another pattern forming method, a conductive pattern material using a photoresist is also known. This method is a method in which a substrate coated with a photoresist polymer or a photoresist on a dry film is exposed to UV 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.
In recent years, with the progress of micromachine development and the further miniaturization of VLSI, these wiring structures have been required to be fine in nano units, and there is a limit to miniaturization in conventional metal etching. There is also concern about disconnection during processing of the thin wire portion.

Further, not only such a continuous metal thin film but also a metal fine particle pattern in which metal fine particles are selectively adsorbed to a specific region has attracted attention.
In recent years, along with the development of an advanced information society, there has been a remarkable increase in the development of electronic devices. In particular, in the development of computer technology that supports the development of an advanced information society, high integration of semiconductor LSIs is Of course, increasing the recording density of magnetic disks is also a major factor. In order to increase the recording density of a magnetic disk, it is required that the magnetic property medium layer has a minimal defect and a high smoothness. For these purposes, currently, a film in which metal fine particles having magnetic properties are dispersed on the surface of a substrate is used, and it is further known that recording capacity can be increased by patterning the metal fine particles. . That is, it is also important to provide the metal fine particle adsorption region in a pattern, but the formation of fine metal fine particle patterns that can respond to the improvement in recording density has the same problem as the metal thin film pattern. Therefore, it is difficult to form a fine metal particle pattern with high resolution.
JP 2004-31588 A

The object of the present invention, which has been made in consideration of the above-mentioned disadvantages of the prior art, is to form a conductive pattern material and a conductive pattern having a wide range of applications, by forming a highly conductive region in a fine pattern with high resolution. It is to provide a method. In addition, another object of the present invention is to provide a conductive pattern material and a conductive pattern forming method suitable for forming a material that requires high conductivity and a fine and high resolution pattern formation such as an electromagnetic wave shield. There is.
Another object of the present invention is to have a metal fine particle adsorption layer in which metal fine particles are dispersed in high density, and the metal fine particle dispersed layer having excellent adhesion and durability is formed in a desired pattern with a fine and high resolution. The object is to provide a thin film, and furthermore, to provide a method for producing a metal fine particle pattern having high productivity and capable of producing a metal fine particle pattern having the above-described characteristics by a simple process.

  As a result of intensive studies, the present inventors have applied graft polymers that are directly bonded to the substrate surface through covalent bonds via a linking portion that includes a specific photocleavage site. The present invention has been completed by finding that the above object can be achieved by a simple process of applying a metal ion or metal salt to an existing region and then reducing the metal ion or metal ion in the metal salt. .

  That is, the conductive pattern material and the metal fine particle pattern material of the present invention have a surface graft having a graft polymer chain that is directly bonded by covalent bond at one end to a substrate surface through a site that can be photocleavable. After exposing the material, cleaving the photocleavable site in the exposed area, removing the graft polymer chain on the surface to form the existing area / absent area of the graft polymer chain, and then the existing area of the graft polymer chain A metal ion or a metal salt is added to the metal ion, the metal ion in the metal salt or the metal ion in the metal salt is reduced to precipitate a metal, and further heated as desired to form a metal thin film, or the metal by the reduction It is characterized by depositing fine particles to form a metal fine particle adsorption region.

As a method (pattern formation method) for forming a pattern comprising a graft polymer chain existing region on a substrate surface, which is preferably applied to the conductive pattern material and the metal fine particle pattern material of the present invention, the following method is used. Can be mentioned.
That is, the graft pattern forming method according to the present invention exposes a surface graft material having a graft polymer chain formed by covalent bonding at one end through a site that can be photocleavable, and photocleavage in the exposed region. This is a method of forming a graft polymer chain existing region / absent region by cleaving a possible site and removing the graft polymer chain. According to this method, an arbitrary high-resolution pattern is formed according to the accuracy of imagewise exposure. Can be formed. A metal thin film or metal fine particle adsorption region is formed according to the pattern of the region where the graft polymer chain exists.

  The conductive pattern forming method and the metal fine particle pattern material of the present invention include a step of forming a pattern composed of a graft polymer chain existing region on the substrate surface by the above-mentioned method, and a metal in the formed graft polymer chain existing region. A step of applying ions or a metal salt, and reducing the metal ions or metal ions in the metal salt to deposit a metal in the form of either a metal thin film or a metal fine particle, thereby providing an adsorption region for the metal thin film or the metal fine particle. Forming. Here, when forming a conductive pattern, you may have the heating process in the temperature range of 100-400 degreeC after the reduction | restoration process of a metal ion.

As another aspect of the present invention, the substrate surface has a functional group that interacts with the electroless plating catalyst or its precursor, and is directly bonded by covalent bond at one end via a site that can be photocleavable. After the surface graft material having the graft polymer chain is exposed, the photocleavable site is cleaved in the exposed region, and the graft polymer chain is removed to form the existing region / absent region of the graft polymer chain. An electroless plating catalyst or a precursor pattern thereof is provided with an electroless plating catalyst or a precursor thereof, and then electroless plating is performed to form a metal thin film.
In addition, as a method for easily forming such a conductive pattern, the substrate surface has a functional group that interacts with an electroless plating catalyst or a precursor thereof, and is capable of photocleavage at one end. The surface graft material having a graft polymer chain directly bonded by a covalent bond is exposed, and in the exposed area, the photocleavable site is cleaved, and the graft polymer chain is removed to thereby present / not present the graft polymer chain. A step of forming a region, a step of applying an electroless plating catalyst or a precursor thereof to a region where a graft polymer chain is present as an electroless plating catalyst or a precursor receiving region thereof, and electroless plating to form a metal thin film And a step of forming a conductive pattern.

  In the present invention, the specific surface graft material having the photocleavage site is used, the graft polymer chain is removed in the exposed region, and the region where the graft polymer chain is present becomes the adsorption region for the metal thin film or metal fine particles. Therefore, a high-resolution metal (fine particle) adsorption pattern can be obtained by scanning exposure based on digital data or pattern exposure using a predetermined mask pattern.

In the surface graft material, the graft polymer chain is bonded to the support at the end thereof directly via a structure having a photocleavage site or via a trunk polymer compound. A metal ion or a metal salt is imparted to the existing region of the graft polymer chain formed by direct bonding to the metal polymer, and a metal is deposited by reducing the metal ion in the metal ion or the metal salt. Since the metal fine particle adsorption region in which the metal fine particles are dispersed and adsorbed in the region is formed, the metal thin film or the metal fine particle adsorption region shows high strength and wear resistance, and is continuous. Similarly, a portion where a wiring is formed by forming a metal layer also exhibits high strength and wear resistance.
In another aspect of the present invention, a functional group that interacts with the electroless plating catalyst or its precursor is introduced into the graft polymer chain in place of a functional group having an affinity with a metal ion or metal salt such as a hydrophilic group. By forming an electroless plating catalyst or its precursor receptive region in a pattern, and applying the electroless plating catalyst or its precursor to the electroless plating catalyst or its precursor receptive region, then electroless plating In the same manner as in the above embodiment, the graft polymer chain having a functional group that interacts with the electroless plating catalyst or its precursor is bonded to the base material. The metal thin film exhibits high strength and wear resistance, and similarly exhibits high strength and wear resistance in the portion where the wiring is formed by the continuous metal layer formation. .

  As a result, even a thin layer can form a high-definition and high-strength metal thin film or metal fine particle adhesion pattern, and the metal salt has an affinity for a metal ion or metal salt such as a hydrophilic group. Ionically adheres (adsorbs) to the functional group, and the adsorbed molecules are firmly fixed. Therefore, a thin and high-strength metal region is formed. It is considered that a fine wiring pattern having no wiring can be formed.

In the present invention, the method for imparting metal ions and / or metal salts in the first aspect includes (1) a metal ion in an existing region of a graft polymer chain comprising a compound that is hydrophilic and has an ionic group. (2) A method of impregnating a region where a graft polymer chain made of a compound having a high affinity for a metal salt such as polyvinylpyrrolidone is impregnated with a metal salt or a solution containing the metal salt ( 3) A method of roughly impregnating a region containing a graft polymer chain with a solution containing a metal salt or a solution in which the metal salt is dissolved. In addition, according to the aspect of said (3), even if the compound which forms the presence area | region of a graft polymer chain has a positive charge, a required metal ion or metal salt can be provided.
In particular, in the present invention, when the third pattern forming method using a compound that can be directly bonded to the support surface is used, the functional group having affinity with a metal ion or metal salt such as a hydrophilic group is: The amount of metal ions or metal salts that can be adsorbed per unit area is extremely high compared to the case where metal salts are adsorbed to a general crosslinked polymer film because of the highly mobile graft chain structure. Has the feature of increasing.
Therefore, the metal adsorption amount is controlled so as to form a continuous metal thin film layer, or a continuous metal layer is formed by fusing adjacent metal particles by heating a high-density metal particle adsorption layer. In such a case, a fine wiring pattern can be formed, and if such a wiring is formed, conductivity is not hindered or disconnected by a gap existing between the metals. In the conductive pattern material of the present invention, while maintaining the formability of fine wiring, it is possible to make the pattern formation layer thinner and achieve higher sensitivity, and the graft polymer chain that forms the pattern. Has a function of directly chemically bonding to the support, and therefore has an advantage of excellent durability even in a thin layer. Further, by the same action, the metal fine particle pattern material of the present invention also has an advantage of excellent durability even if the metal fine particle adsorption layer is a thin layer.

ADVANTAGE OF THE INVENTION According to this invention, the electroconductive pattern material and electroconductive pattern formation method with a wide application range which form a highly conductive area | region in the pattern shape with a fine and high resolution can be provided. Such a conductive pattern material of the present invention is suitable as a material that requires an arbitrary pattern formation with high conductivity, fineness, and high resolution, such as an electromagnetic wave shield, and the conductive pattern material method of the present invention. Therefore, such a conductive pattern material can be easily manufactured.
In addition, according to the present invention, a thin metal film having a fine metal particle-adsorbing layer in which a fine metal particle dispersion layer in which fine metal particles are dispersed at high density and excellent in adhesion and durability is formed in a desired pattern with a fine and high resolution. Furthermore, according to the method of the present invention, the metal fine particle pattern having the above characteristics can be produced by a simple process with high productivity.

The conductive pattern material and metal fine particle pattern material of the present invention will be described in detail below.
The conductive pattern material and the metal fine particle pattern material of the present invention are base materials having a graft polymer chain that is directly bonded to the base material surface at one end by a covalent bond, and the graft polymer chain is photocleavable. A surface graft material that is covalently bonded to the substrate surface through a possible site, cleaves the photocleavable site in the exposed area, removes the graft polymer chain, and presents / not present the graft polymer chain. After forming the existence region, a metal ion or a metal salt is added to the existence region of the graft polymer chain, and the metal ion or the metal ion in the metal salt is reduced to form a metal thin film or metal fine particle adsorption region. It becomes.
Hereinafter, a method (pattern forming method) for forming a pattern composed of a graft polymer chain existing region on the substrate surface will be described.

What is used for pattern formation in the present invention is a surface graft material having a graft polymer chain which is directly bonded to the substrate surface at one end by a covalent bond, and the graft polymer chain has a photocleavable site. It is a surface graft material that is covalently bonded to the surface of the substrate.
Such a surface graft material is produced by heating in a state where the monomer is in contact with the surface of the substrate, or by causing a polymerization reaction using a catalyst to generate a whole surface graft polymer on the surface of the substrate. The At this time, a homopolymer that is not bonded to the surface of the base material is also formed as a by-product, but the surface graft material is obtained by removing and purifying the homopolymer after the surface graft formation.

The conductive pattern material, metal fine particle pattern material, and surface graft material used in the pattern forming method of the present invention are characterized by the bonding portion between the base material and the graft polymer chain, and the surface having such a bonding portion. The following two methods are mentioned as a representative method of graft formation.
(1) Method of modifying the substrate surface This method first modifies the substrate surface by introducing a specific linking site having an initiation ability at the end of the substrate surface, and then the initiation ability is changed. This is a method for generating a graft starting from a portion having the same.
Here, a functional group (hereinafter referred to as Z) present on the substrate surface is used as a starting point for introducing a specific compound (QXY) described later for forming a graft polymer. Z will be described in detail below, but it may be a functional group present on the surface of the base material from the beginning, or a functional group generated by subjecting the base material to a surface treatment such as corona discharge. This functional group (Z) has a base material binding group (Q) having a binding ability to the base material at both ends and a polymerization initiating group (Y), and a photocleavage site (X ) Is introduced by bonding the base material binding group (Q) and the functional group (Z) on the surface of the base material. Thereafter, a known graft polymer raw material such as a monomer is brought into contact with this surface, and a graft polymer chain is generated starting from the polymerization initiation group (Y) of the introduced compound (Q-XY) to obtain a surface graft material.

(2) Method of using a polymer having a specific linking site A polymer in which a specific linking site having a binding ability to a substrate is introduced at the terminal is prepared in advance, and a graft polymer is used as a base material by using the binding capability of the polymer A method of bonding to a surface.
In the method of (2), a base material binding group (Q) having a binding ability to a base material at both ends and a polymerization initiating group (Y) are previously provided, and photocleavage is performed between the both ends. A polymer in which a graft polymer chain is generated from the polymerization initiation group (Y) of the compound (QXY) having the site (X) is produced and used. That is, a graft polymer chain having such a (Q-X-Y) terminal structure is prepared, and then the obtained polymer having a linking site is present on the substrate binding group (Q) and the substrate surface. The surface graft material is obtained by linking by bonding to the functional group (Z).

Hereinafter, a process for producing such a surface graft material will be specifically described.
The group represented by Z is a functional group present on the surface of the substrate, and specific examples 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.
Next, the structure of the compound having a photocleavage site will be specifically described.
Compound (Q-X) having a substrate binding group (Q) having a binding ability to a substrate at both ends and a polymerization initiating group (Y), and having a photocleavage site (X) between both ends If it explains in detail using a model of -Y), generally X is a part containing a single bond (single bond) which can be cleaved by light.
Q is a reactive group that can react and bond with the functional group Z present on the surface of the substrate, and specific examples thereof include the following groups.

  Y is a polymerization initiating group, but in order to effectively develop the characteristics of the photocleavage site, in the present invention, a polymerization initiating group that initiates polymerization by a method other than light is selected. Y includes functional groups such as thermal polymerization initiation sites or living radical initiation sites such as atom transfer polymerization, RAFT polymerization, and iniferter polymerization, and more specifically, the following groups are exemplified.

Examples of the photocleavage site represented by X include those utilizing carbonyl α-cleavage, β-cleavage reaction, light-free rearrangement reaction, benzyl ester rearrangement reaction, and phenacyl ester cleavage reaction. The single bond (single bond) that can be cleaved by is broken. Examples of utilizing such a reaction include the following photocleavage site examples 1 to 4, and a single bond at a portion indicated by a wavy line in the structure is cleaved.
As another example of X, a site capable of cleavage by incorporating a bond cleavage reaction such as sulfonimide cleavage reaction, sulfonyl ester cleavage reaction, N-hydroxysulfonyl ester cleavage reaction, α-ketosulfonate cleavage reaction, ketosulfone cleavage reaction, etc. The following photocleavage site examples 5 to 10 are exemplified as those utilizing this cleavage, and a single bond at a portion indicated by a wavy line in the structure is cleaved.

Specific examples of the compound (QXY) having a substrate binding group (Q) and a polymerization initiating group (Y) and having a photocleavage site (X) between both ends [Exemplary compounds 1 to Illustrative compound 10] is shown below together with reaction mechanisms such as functional groups, but the present invention is not limited thereto.
Such compounds can be synthesized by various methods. For example, a method of linking a photocleavage site and a polymerization initiation site, and finally linking a substrate binding group, linking a substrate binding group and a polymerization initiation site, and simultaneously introducing a photocleavage group into the binding site And a method of bonding a polymerization initiation site after bonding a substrate binding site and a photocleavage site.

In the method (1), the base material binding group Q of such a compound (Q-XY) is introduced into the base material surface by binding to the functional group Z present on the base material surface, and then known. According to the method, the surface graft material of the present invention can be obtained by generating a graft starting from the polymerization initiating group Y.
When the compound (Q-XY) as exemplified is bonded to the functional group Z present on the substrate surface and introduced to the surface, the compound (Q-X-Y) is appropriately selected from toluene, hexane, acetone, etc. This method is called a chemical adsorption method in which it is dissolved or dispersed in a suitable solvent and brought into contact with the substrate surface, or a gas phase method in which the compound (QXY) is heated and vaporized to react with the substrate surface. A method may be applied. In addition, the heating temperature when applying the vapor phase method is preferably in the range of 50 to 300 ° C. Moreover, when applying a chemical adsorption method, it is preferable that the density | concentration of the compound (QXY) in a solvent is 0.01-10 mass%, and the liquid temperature in making it contact is 0-100 degreeC, The contact time is preferably 1 minute to 50 hours.

  Thus, after introduce | transducing a compound (QXY) on the base-material surface, as a production | generation method of the graft | grafting which makes the polymerization initiating group Y a base point, compound (Q-) fixed on the base material is mentioned, for example. XY) is usually immersed in a dispersion in which a monomer having a hydrophilic functional group is dissolved and dispersed together with the base material, and energy is applied by means other than light irradiation. The initiating group Y is activated, and a grafting reaction occurs and proceeds with a compound (for example, a hydrophilic monomer) having a polymerizable group present in the liquid.

A more specific embodiment of the surface graft polymerization will be described. In the present invention, the graft polymer chain needs to have a functional group having an affinity with a metal ion or a metal salt or a functional group that interacts with an electroless plating catalyst or a precursor thereof described later, A specific example of a functional group having an affinity for a metal ion or metal salt will be described specifically by taking a group having a hydrophilic group as an example.
(Hydrophilic monomer having a polymerizable group)
In the present invention, a hydrophilic monomer having a polymerizable group (hereinafter referred to as a polymerizable group-containing hydrophilic monomer) used for producing a graft polymer for adhesion of conductive materials and metal fine particles is a vinyl group, It refers to a monomer having a hydrophilic functional group as a functional group into which an ethylene addition polymerizable unsaturated group such as an allyl group or a (meth) acrylic group is introduced and has an affinity for a metal ion or a metal salt.
Examples of the hydrophilic functional group include a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, an amino group and a salt thereof, an amide group, a hydroxyl group, an ether group, and a polyoxyethylene group.

  Specific examples of the polymerizable group-containing hydrophilic 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 alkali metal salts and amine salts thereof, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or salts thereof, 2-dimethylaminoethyl (meta Acrylate or its hydrohalide, 3-trimethylammoniumpropyl (meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) Ammonium chloride, etc. can be used. In addition, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) ) Acrylate is also useful.

(Solvent for compound solution having polymerizable group)
The solvent for dissolving and dispersing the compound having a polymerizable group described above is not particularly limited as long as the compound having a polymerizable group and an additive added as necessary can be dissolved. An aqueous solvent such as an ionic solvent is preferable, and a mixture thereof or a solvent obtained by further adding a surfactant to the solvent is preferable.
The water-soluble solvent refers to a solvent miscible with water in an arbitrary ratio, and examples of such a water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerin, acids such as acetic acid, Examples thereof include ketone solvents such as acetone, amide solvents such as formamide, and the like.

(Energization to generate graft polymer)
In the present invention, as a method of bringing a compound having a polymerizable functional group into contact with a substrate on which a specific compound (QXY) containing a polymerization initiating group Y is immobilized, the above-described hydrophilic monomer is dissolved, A method of immersing the substrate in the dispersed solution is generally used, but from the viewpoint of the handleability and production efficiency of the conductive pattern material and the metal fine particle pattern material, a polymerizable hydrophilic compound is used. You may carry out by forming the layer which has a composition which contains it as a main component on the support body surface by the apply | coating method. Thus, by giving energy in the state which contacted both, a polymerization reaction arises and advances between the polymerization initiating group Y and the compound which has a polymerizable functional group.

In the method of the present invention, there is no particular limitation on the energy application method for generating the graft polymer in the polymerization initiation layer, and any method that can provide energy that can decompose and activate the initiator in the polymerization initiation layer, Although methods such as a thermal polymerization method using a thermal head, a heater, and an atom transfer radical polymerization method using a metal complex can be used, the polymerization method by heating is preferred from the viewpoint of cost and simplicity of the apparatus. More specifically, examples of the heat polymerization method include radical generation by thermal decomposition of an azo group and the like, radical generation by heat of nitrogen oxides such as nitrooxime, and the electron transfer radical polymerization method includes a cobalt / polyfin complex. Examples thereof include a method of generating radicals by reacting radicals generated by heat, such as generation of radicals by heat, iodine transfer polymerization, and raft polymerization. These methods are described in Takeshi Fukuyama, “Polymer” Vol. 48, page 498 (1999), and the described methods can be used as appropriate in the present invention.
When such a graft polymer chain is imparted with functions such as hydrophilicity and adsorptivity to other substances, a monomer having a desired functional group may be used as a monomer used to generate the graft chain. .

That the thickness of the graft layer formed by graft polymer produced as described above is preferably in the range of 0.001 to 10 g / m ^2, in the range of 0.01-5 g / m ² More preferred.

In addition, the specific polymer used in the method (2) causes a polymerization reaction to start from the polymerization initiating group Y of the compound (QXY), forms a polymer chain starting from Y, and has one end. A polymer having a substrate binding group Q that can bind to a substrate is prepared, and then the substrate binding group Q is bonded to a functional group Z present on the substrate surface to obtain a surface graft material.
Specific examples of the specific polymer prepared using the compound (QXY) as a starting material are shown below.

Such a specific polymer is prepared by synthesizing a polymer using a terminal thiol carboxylic acid as a chain transfer agent, introducing a carboxy group at the end of the polymer, and linking it to the remaining portion, specifically, a photocleavage site and a substrate binding group. Can be obtained at As another method. It can be synthesized using atom transfer polymerization from the photocleavage site and the terminal of the benzyl chloride group linked to the substrate binding group.
Examples of the method for introducing the polymer linked to the compound (QXY) onto the substrate surface include the same chemical adsorption method and gas phase method as those for introducing the compound (QXY). Of these, from the viewpoint of production suitability, it is preferable to employ a method by chemical adsorption.
The thickness of the graft layer formed by the method (2) as described above is preferably in the range of 0.1 mg / m ^{2 to} 10 g / m ² , and preferably 1 mg / m ^{2 to 5} g / m ² . A range is more preferable.

  As for the surface graft material of the present invention thus obtained, the graft polymer chain is directly bonded to the surface of the substrate through the photocleavage site (X). Unless light irradiation capable of cleaving a predetermined single bond at the photocleavage site is performed, the graft polymer chain is firmly bonded to the substrate surface.

[Base material (support)]
The conductive pattern material of this aspect and the base material (sometimes referred to as a support) used for the metal fine particle pattern material are a surface graft layer chemically bonded via the aforementioned photocleavage site and the graft polymer. The chain has a surface that can be chemically bonded directly or through a trunk polymer compound, and further, a specific compound (QXY) or a specific polymer (QXY Polymer) in the present invention. ) Having a functional group Z (for example, a hydroxyl group, a carboxyl group, an amino group, etc.) that can react (bond) with the substrate binding group Q. Specifically, organic polymers such as epoxy, acrylic, polyimide, and urethane can be used as the substrate in addition to substrates such as glass, silicon, and aluminum. Further, in the case of an organic polymer base material, it is preferable to perform glow treatment or plasma treatment in order to form the group represented by Z on the surface. In addition, the surface of the base material itself may have such characteristics, and an intermediate layer having such characteristics may be provided as a support (base material).

[Pattern formation and metal (fine particle) film formation]
Next, pattern formation of the conductive pattern material and metal fine particle adsorption pattern material obtained in this way, and a metal thin film region or metal fine particle adsorption region (hereinafter referred to as a metal (fine particle) film as appropriate) to the pattern. Will be described.
In the pattern forming mechanism of the conductive pattern material of this aspect and the metal fine particle pattern material, the surface graft material obtained as described above is exposed to form a pattern to form a hydrophilic group of the graft polymer chain, etc. Depending on the function, metal ions and metal salts are adsorbed due to their ion adsorption properties, etc., depending on their functions. Then, by reducing the adsorbed metal ions, a metal simple substance is deposited in the region, a metal thin film is formed, or the adsorbed metal ions or metal ions in the metal salt are reduced to reduce the metal in the region. A single substance is deposited, a metal thin film is formed, and further, a metal film is formed by an electroless plating process by the action of an electroless plating catalyst (precursor). As a result, a metal (fine particle) film is formed, and when the formed metal (fine particle) layer is a continuous layer, a conductive region is formed. In the region where the graft polymer chain does not exist, metal ions, metal salts, and electroless plating catalyst (precursor) are not adsorbed and impregnated, and a metal (fine particle) film is not formed. Therefore, when the metal thin film becomes a conductive region, this region becomes a non-conductive insulating region.

(writing)
The image-like (pattern) writing on the surface graft material according to the present invention will be described. When the surface graft material of the present invention is subjected to pattern exposure, as described above, a predetermined single bond existing in the photocleavage site X is cleaved in the exposed portion, and the graft polymer chain in the exposed region is released from the bond. Separate from the material. At this time, since there is no excess homopolymer in the vicinity, the graft polymer in the exposed portion is easily removed. This also applies to a fine image portion, and a desired high-resolution graft pattern corresponding to the exposure pattern is formed.

The resolution of the graft pattern at this time depends on the exposure conditions. There are no particular limitations on the exposure method that can be used in the graft pattern forming method of the present invention, and ultraviolet light or visible light may be used as long as it can provide energy that causes cleavage at the photocleavage site X.
Preferred exposure light sources include ultraviolet light and deep ultraviolet light.
Moreover, if the graft | grafting surface material of this invention is used, high-resolution pattern formation is possible, and the high-definition pattern according to exposure will be formed by performing pattern exposure for high-definition image recording. 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 an i-line stepper, KrF stepper, and ArF stepper.

  After the exposure, the surface graft material is washed with a solvent such as pure water or acetone in order to remove the graft polymer chains cut in the exposed region. According to the method of the present invention, since no extra homopolymer is present in the vicinity of the surface graft region, the graft polymer cut at the exposed portion is used for general purpose cleaning such as running water cleaning, immersion cleaning, and ultrasonic cleaning. It is easily removed by taking measures.

[Formation of metal (fine particle) film]
After the pattern of the existing region of the graft polymer chain is formed by the above method, in one embodiment, a metal ion or a metal salt is applied to the region, and the metal ion in the metal ion or the metal salt is further added. To form a metal thin film or metal fine particle adsorption region.
The method for imparting the metal ion or metal salt can be appropriately selected depending on the compound forming the existence region of the graft polymer chain. Specifically, (1) when the compound forming the existence region of the graft polymer chain is a hydrophilic compound and has an ionic group, a method of adsorbing metal ions in that region, (2) the graft polymer chain A method of impregnating a metal salt or a solution containing a metal salt in the region when the compound forming the existing region is a compound having a high affinity for the metal salt such as polyvinylpyrrolidone; (3) Grafting A method of immersing a region where a polymer chain exists in a solution containing a metal salt or a solution in which the metal salt is dissolved, and impregnating the region with a solution containing a metal ion and / or a metal salt; Any method of forming a metal film by performing an electroless plating process on the region where the chain is present in the following manner can be appropriately selected and used. In particular, according to the method (3), since the properties of the compound are not particularly limited, a desired metal ion or metal salt can be imparted.

<Metal ions and metal salts>
Next, metal ions and metal salts will be described.
In the present invention, the metal salt is not particularly limited as long as it is dissolved in a suitable solvent to be applied on the hydrophilic surface and can be dissociated into a metal ion and a base (anion). 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. Ag is preferably used as the conductive film and Co is preferably used as the magnetic film.

  When applying a metal ion or a metal salt to a hydrophilic region, (1) When a compound that forms an existing region of a graft polymer chain has an ionic group and uses a method of adsorbing a metal ion in that region The above-mentioned metal salt is dissolved in a suitable solvent, and the solution containing the dissociated metal ions is applied to the substrate surface having the existing region of the graft polymer chain, or the graft polymer chain is dissolved in the solution. A substrate having an existing region may be immersed. By bringing a solution containing metal ions into contact, metal ions can be ionically adsorbed to the ionic functional group. From the viewpoint of sufficiently performing these adsorptions, the metal ion concentration or the metal salt concentration of the solution to be contacted is preferably in the range of 1 to 50% by mass, and more preferably in the range of 10 to 30% by mass. preferable. The contact time is preferably about 1 to 24 hours.

  When applying a metal ion or metal salt to the existing region of the graft polymer chain, (2) the compound forming the existing region of the graft polymer chain has a high affinity for the metal salt such as polyvinylpyrrolidone. In the case of using a method in which the metal salt or a solution containing the metal salt is impregnated in the region, the metal salt is directly attached in the form of fine particles, or an appropriate metal salt can be dispersed. A dispersion may be prepared using a solvent, and the dispersion may be applied to a substrate surface having a graft polymer chain existing region, or the substrate having the region may be immersed in the solution. Since the pattern formed in the present invention consists of a graft polymer, its water retention is very high. Utilizing the high water retention property, the dispersion region in which the metal salt is dispersed can be impregnated in the existing region of the graft polymer chain. From the viewpoint of sufficiently impregnating the dispersion, the metal salt concentration or the metal salt concentration of the dispersion to be contacted is preferably in the range of 1 to 50% by mass, and in the range of 10 to 30% by mass. More preferably. The contact time is preferably about 1 to 24 hours.

  When a metal ion or a metal salt is applied to an existing region of the graft polymer chain, (3) the substrate having the existing region of the graft polymer chain is immersed in a solution containing the metal salt or a solution in which the metal salt is dissolved. Then, when using a method of impregnating a solution containing metal ions and / or metal salts using the hydrophilicity of the graft polymer chain, the dispersion is prepared using an appropriate solvent in which the metal salts can be dispersed. Or prepared by dissolving the above metal salt in a suitable solvent to prepare a solution containing dissociated metal ions, and applying the dispersion or solution to the substrate surface having the existing region of the graft polymer chain. Alternatively, a substrate having the region may be immersed in the solution. In such a method, similarly to the above, the dispersion or solution can be impregnated in the region by utilizing high water retention in the region where the graft polymer is present. From the viewpoint of sufficiently impregnating the dispersion or solution, the metal salt concentration of the dispersion to be contacted, or the metal salt concentration 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 1 to 24 hours.

[Reducing agent]
In the present invention, the metal salt used by adsorbing or impregnating the existing region of the graft polymer chain, or the reducing agent used to form a metal (fine particle) film by reducing metal ions is used as the reducing agent. There is no particular limitation as long as it has the physical property of reducing a salt compound and precipitating a metal, and examples thereof include hypophosphite, tetrahydroboronate, hydrazine and the like.
These reducing agents can be appropriately selected in relation to the metal salt and metal ion to be used. For example, when a silver nitrate aqueous solution or the like is used as the metal salt aqueous solution for supplying the metal ion or metal salt, tetrahydroboron is used. When sodium acid uses an aqueous palladium dichloride solution, hydrazine is preferred.

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

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

[Relationship between polarity of functional group of graft polymer chain and metal ion or metal salt in surface graft polymerization]
If the graft polymer chain constituting the graft pattern has a functional group having a negative charge, metal particles having a positive charge are adsorbed here, and the adsorbed metal ions are reduced to deposit metal fine particles. A region to be formed (conductive region: wiring when a continuous layer is formed) is formed.

[Relationship between the polarity of the hydrophilic group of the hydrophilic compound binding type and the metal ion or metal salt]
When the graft polymer chain constituting the graft pattern has an anionic property such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group as the hydrophilic functional group as described in detail above, the pattern portion is selectively selected. A metal (fine particle) film region (for example, a wiring) is formed by adsorbing a metal ion having a positive charge and reducing the adsorbed metal ion.
On the other hand, when the graft polymer chain constituting the graft pattern has a cationic group such as an ammonium group described in JP-A-10-296895, the pattern portion selectively has a positive charge. A metal (fine particle) film region (wiring) is obtained by impregnating a metal salt-containing solution or a solution in which the metal salt is dissolved into the metal salt and reducing metal ions present in the impregnated solution or metal ions in the metal salt. ) Is formed.
It is preferable from the viewpoint of durability that these metal ions are bonded in the maximum amount that can be imparted (adsorbed) to the hydrophilic group on the hydrophilic surface.

  As a method for imparting a metal ion to an ionic group, a solution in which a metal ion or a metal salt is dissolved or dispersed is applied to the surface of a substrate having a graft polymer chain (graft pattern) formed in the above-described manner. The method of apply | coating, the method of immersing the base-material surface in which the graft pattern was formed in these solutions or dispersion liquid etc. are mentioned. In either case of coating or dipping, an excessive amount of metal ions is supplied and introduced by a sufficient ionic bond between the functional groups having affinity for metal ions or metal salts. The contact time between the dispersion and the support surface is preferably about 10 seconds to 24 hours, more preferably about 1 minute to 180 minutes.

The metal ion is not limited to one type, and a plurality of types can be used in combination as required. In order to obtain desired conductivity, a plurality of materials can be mixed and used in advance.
The pattern portion of the metal fine particle pattern produced in the present invention is tightly dispersed in the surface graft film by surface observation and cross-sectional observation by SEM and AFM. The size of the metal fine particles to be produced is 1 nm to 1 μm in particle size.
The metal thin film pattern produced by the above method can be used as a conductive pattern as it is, but from the viewpoint of improving the film properties and improving the conductivity, it is preferable to perform a heat treatment described later. In addition, when a metal fine particle pattern is used as a conductive pattern material, it can be used as it is as a conductive pattern when the metal fine particles are closely adsorbed and apparently form a metal thin film. From the viewpoint of ensuring good electrical conductivity, it is preferable to further heat-treat the formed metal fine particle pattern.
The heating temperature in the heat treatment step is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably about 200 ° C. The heating temperature is preferably 400 ° C. or lower in consideration of the processing efficiency and the dimensional stability of the support substrate. In addition, the heating time is preferably 10 minutes or more, and more preferably about 30 minutes to 60 minutes. Although the mechanism of action by heat treatment is not clear, in the case of a metal film, the composition and film thickness uniformity in the film are improved, and in the metal fine particle adsorption region, some adjacent metal fine particles melt together. It is thought that the conductivity improves by wearing.

Further, (4) a method of performing an electroless plating process, which is a method of forming a further metal pattern, specifically includes (4-1) an electroless plating catalyst or an electroless plating catalyst in an existing region (graft pattern) of a graft polymer chain. There is a method in which a precursor is applied and then (4-2) electroless plating is performed to form a metal film in a pattern. These will be described in the order of steps.
[(4-1) Step of imparting electroless plating catalyst or precursor thereof to graft pattern]
<Electroless plating catalyst>
The electroless plating catalyst used in this step is mainly a zero-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable because of their good handleability and high catalytic ability. As a method of fixing the zero-valent metal on the graft pattern (interactive region), for example, a functional group (interactive group) that interacts with the electroless plating catalyst (precursor) on the graft pattern, A technique is used in which a metal colloid whose charge is adjusted so as to interact is applied to the interactive region. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here, and the metal colloid having the charge adjusted as described above is interacted with the interactive group of the graft pattern. The metal colloid (electroless plating catalyst) can be selectively adsorbed onto the graft pattern.

<Electroless plating catalyst precursor>
The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion that is an electroless plating catalyst may be used as an electroless plating catalyst after being applied to a substrate and before being immersed in an electroless plating bath, by changing it to a zero-valent metal by a reduction reaction. The 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 fact, the metal ions that are the electroless plating precursors are imparted to the graft pattern in the form of a metal salt and interact with each other. The metal salt used is not particularly limited as long as it is dissolved in an appropriate solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.

  As a method for applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor onto a graft pattern, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is added with an appropriate solvent. A solution containing dissolved and dissociated metal ions is prepared, and the solution is applied to the surface of the substrate on which the graft pattern exists, or the substrate having the graft pattern is immersed in the solution. Contacting a solution containing a metal ion to adsorb a metal ion to the interacting group of the graft pattern forming region using an ion-ion interaction or a bipolar-ion interaction; or The interaction region can be impregnated with metal ions. From the viewpoint of sufficient adsorption or impregnation, the metal ion concentration or metal salt concentration of the solution to be contacted is preferably in the range of 1 to 50% by mass, and in the range of 10 to 30% by mass. Is more preferable. Further, the contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour.

[(4-2) Step of performing electroless plating and forming a metal film in a pattern]
Next, a metal film is formed in a pattern by performing electroless plating on the substrate obtained in the step (4-1). By performing electroless plating in this step, a high-density metal film according to the pattern is formed on the graft pattern obtained in the step. As a result, the formed metal pattern has excellent conductivity and adhesion.

<Electroless plating>
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
In the electroless plating in this step, for example, the substrate provided with the electroless plating catalyst in a pattern shape obtained in the step (4-1) is washed with water to remove excess electroless plating catalyst (metal). Thereafter, it is immersed in an electroless plating bath. As the electroless plating bath to be used, a generally known electroless plating bath can be used.
Further, when the substrate to which the electroless plating catalyst is applied in a pattern is immersed in the electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the graft pattern, the substrate is washed with water to remove the excess. After removing the electroless plating catalyst precursor (metal salt, etc.), it is immersed in an electroless plating bath. In this case, the precursor is reduced in the electroless plating bath, followed by electroless plating. As the electroless plating bath used in this embodiment, 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 thickness of the metal film formed in this way can be controlled by the concentration of the metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, etc. Is preferably 0.5 μm or more, 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 metal film portion of the metal pattern obtained as described above, the electroless plating catalyst and the fine particles of the plating metal are tightly dispersed in the surface graft film by cross-sectional observation by SEM, and further, there are relatively It was confirmed that large particles were precipitated. Since the interface is a hybrid state of the graft polymer and fine particles, even if the unevenness of the interface between the substrate (including organic components) and the inorganic material (electroless plating catalyst or plating metal) is 100 nm or less, the adhesion Was good.

[Electroplating process]
In the conductive pattern forming method using electroless plating in the present invention, when the metal film is formed by using this (4) electroless plating treatment, the metal film formed by the above process is then used as an electrode. Electroplating can be performed. As a result, a metal film having an arbitrary thickness can be easily formed on the metal film pattern having excellent adhesion to the substrate. By adding this step, a patterned metal film can be formed to a thickness according to the purpose, and therefore, the metal pattern of the present invention is suitable for application to various applications such as a wiring pattern.
As the electroplating method in the present invention, a conventionally known method can be used. In addition, as a metal used for the electroplating of this process, copper, chromium, lead, nickel, gold, silver, tin, zinc, etc. are mentioned. From the viewpoint of conductivity, copper, gold, and silver are preferable. More preferred.

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

  The conductive pattern material of the present invention and the metal fine particle pattern material formed by the above method can produce a high-definition metal (fine particle) pattern on the surface of the base material by a simple process, making it durable. It has an excellent high-density metal (fine particle) film pattern. In addition, the conductive pattern material and the metal fine particle pattern of the present invention can be expected to be used in various applications such as a high-density magnetic disk, a magnetic head, a magnetic tape, a magnetic sheet, and a magnetic disk, and its application range is wide. Furthermore, since it can be used for various circuit formation applications and a fine conductive region can be formed by selecting a pattern forming means, a wide range of applications including circuit formation such as micromachines and VLSI is expected. .

Furthermore, when a transparent film such as PET is used for the support, it can be used as a patterned transparent conductive film. Applications of such transparent conductive films include transparent electrodes for displays, light control devices, solar cells, touch panels, and other transparent conductive films, but are particularly useful as electromagnetic wave shielding filters for CRTs and plasma displays. . Since such an electromagnetic wave shielding filter requires high conductivity and transparency, it is preferable to provide a metal (fine particle) film in a lattice shape. Such a lattice line width is preferably about 20 to 100 μm, and the opening is preferably about 50 to 600 μm. This lattice does not necessarily have to be regular and configured with straight lines, and may be configured with curved lines.
In the present invention, a finer pattern having a line width of 10 μm or less can be formed, and a metal wiring or metal fine particle adsorption region having such an arbitrary pattern shape can be easily formed. Various settings are possible.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
(Synthesis Example 1: Synthesis of photocleavable silane coupling compound 1)
The exemplary compound 1 is synthesized by the following four steps. A description will be given of the scheme of each step.
1. Synthesis of ATRP initiator “l” (olefin introduction by etherification (Williamson reaction))
4-hydroxy-4 '-(hydroxyethoxy) -2-methylpropiophenone (22.4 g, 0.1 mol) and tetrahydrofuran (THF) (300 g) were placed in a nitrogen-substituted 1000 ml three-necked flask, cooled with an ice bath, and stirred. did. To this, 9.7 g (0.24 mol) of NaH (60 to 72% in oil) was gradually added. When all the addition was completed, the ice bath was removed and the mixture was stirred for 2 hours. The reaction solution was cooled again with an ice bath, and half of 13.3 g (0.11 mol) of allyl bromide dissolved in 25 g of THF and 25 g of dimethylacetamide (DMAc) was slowly added dropwise. The other half was dropped after 30 minutes. After dropping, the ice bath was removed by stirring for 30 minutes, and 300 g of DMAc was added in 100 g portions (1.5 hours after removing the ice bath, 2.5 hours, and 4 hours later). Stirring was stopped 3 hours after adding the entire amount of DMAc and allowed to stand overnight. A small amount of methanol was added to the reaction solution to crush unreacted NaH. The reaction solution was gradually added to 1500 ml of water. The organic phase in the solution was extracted with ethyl acetate and washed with aqueous sodium chloride solution. The solvent was distilled off to obtain 27 g of a yellow oil containing the product 1a.
A synthesis scheme is shown below.

¹ H NMR (300 MHz CDCl 3)
δ = 1.64 (s, 6H, —CH ₃ k—CH ₃ l), 3.8 (t, J = 4.5-5.1, 2H, —CH ₂ e), 4.1 (d, J = 5.7, 2H, —CH ₂ d), 4.2 (t, J = 4.2-5.4, 2H, —CH ₂ f), 4.3 (s, 2H, —OHm), 5.2 (dd, JHbHc = 10.2-10.7, JHaHb = 0.9-1.2, 1H, Hb.), 5.3 (dd, JHaHc = 17-22, JHaHb = 0.9 -1.2, 1H, Ha.), 5.9 (ddd, JHaHc = 22-17, JHbHc = 10.2-10.7, JHcHd = 5.4-5.7, 1H, Hc), 0 (dd, JHhHi = 7, JHgHj = 7, JHgHh = 2, JHiHj = 2, 2H, HgHi), 8.1 (dd, JHhHi = 7, JHgHj = 7, JH Hh = 2, JHiHj = 2,2H, Hh Hj)

Synthesis of 2.1b (introduction of a long-chain alcohol using a protecting group)
First, 14.4-g (0.069 mol) of 8-bromo-1-octanol and 10 g of THF were placed in a 200 ml eggplant flask, and 7.3 g (0.087 mol) of 3,4-dihydro-2H-pyran was added dropwise with stirring. . Stirring was continued for 30 minutes to obtain a solution A.
Next, 14.5 g (0.055 mol) of yellow oil containing 1a and 100 g of DMAc were placed in a 300 ml three-necked flask and stirred while cooling in an ice bath. NaH (60-72% in oil) 3.3 g (0.083 mol) was gradually added and stirred for 30 minutes. The previously prepared solution A was dropped, and the ice bath was replaced with a water bath and heated at 50 ° C. for 1.5 hours. A small amount of methanol was added to the reaction solution, and then gradually added to 300 ml of ice water. The organic phase was extracted with ethyl acetate and washed with aqueous sodium chloride solution. The solvent was distilled off to obtain a yellow oil. This yellow oil was dissolved in 200 ml of methanol, a small amount of p-toluenesulfonic acid was added, and the mixture was heated at 70 ° C. for 1 hour. Water was added to this solution and the organic phase was extracted with ethyl acetate. The solvent was distilled off to obtain 35.1 g of a brown oil containing the product 1b.
A synthesis scheme is shown below.

Synthesis of 3.1c (introduction of terminal halogen by esterification reaction)
A 1000 ml three-necked flask equipped with a calcium chloride tube was charged with 25.52 g (0.065 mol) of brown oil containing 1b, 200 g of THF and 6.17 g (0.078 mol) of pyridine, and stirred. The solution was cooled in an ice bath, 14.94 g (0.065 mol) of bromoisobutyric acid bromide was gradually added and stirred for 15 minutes, then returned to room temperature and stirred for 1.5 hours. The reaction solution was poured into 300 ml of water. The organic phase was extracted with ethyl acetate and washed with aqueous sodium chloride solution. The solvent was distilled off to obtain 43.9 g of a brown oil containing the product AM2543c. 1c was isolated with a column (filler: Wakogel C-200, developing solvent: ethyl acetate / hexane = 1/5).
A synthesis scheme is shown below.

¹ H NMR (300 MHz CDCl ₃ )
δ = 1.2-1.4 (mb, 8H), 1.5 (s, 6H), 1.7 (t, J = 6.9-7.5, 4H), 1.9 (s, 6H) ), 3.2 (t, J = 6.0-6.9, 2H), 3.8 (t, J = 4.8, 2H), 4.1-4.2 (m, 6H), 5 .2 (dd, J = 1.8, J = 10.2-11.4, 1H.), 5.3 (dd, J = 1.8, J = 17.1-22.5, 1H.) 5.9-6.0 (ddd, J = 5.4-5.7, J = 10.2-11.4, J = 17.1-22.5, 2H), 6.9 (d, J = 9.0, 2H), 8.3 (d, J = 9.0, 2H)

4). Synthesis of target 1 (hydrosilylation reaction)
4.5 g (8.31 × 10 ⁻³ mol) of 1c is placed in a 50 ml three-necked flask equipped with a calcium chloride tube, and 1 drop of Spear catalyst (H ₂ PtCl ₄ .6H ₂ O / 2-PrOH 0.1M) is added. And stirred. The reaction solution was cooled in an ice bath, and 2.4 g (17.46 × 10 ⁻³ mol) of trichlorosilane (98%) was added dropwise. After dropping, the temperature was returned to room temperature, and the reaction was completed after 1 hour. Excess trichlorosilane was removed by heating at 100 ° C. under reduced pressure to obtain the intended product 1.
A synthesis scheme is shown below.

¹ H NMR (300 MHz CDCl ₃ )
δ = 1.2−1.4 (mb, 20H), 1.5 (s, 6H), 1.9 (s, 6H), 3.2 (t, J = 6.9, 2H), 6 (t, J = 6.9, 2H), 4.2 (m, 4H), 6.9 (d, J = 9.3, 2H), 8.3 (d, J = 9.3, 2H) :)

[Example 1]
(Synthesis of graft substrate A (acrylic acid graft))
A silicon substrate cleaned using a Piranha solution (a 1 vol solution of sulfuric acid / hydrogen peroxide (30 wt%)) under argon, a silane coupling agent having an initiator group (the exemplified compound obtained in Synthesis Example 1) The initiator was immobilized on the silicon substrate by immersing in 1.1% by mass dehydrated toluene solution of 1) overnight. Next, the substrate on which the initiator (Exemplary Compound 1) is immobilized is placed in a separable flask and immersed in an aqueous solution of sodium acrylate using copper chloride (I) and 2,2′-bipyridyl as a catalyst in an Ar stream. After stirring, the graft substrate A was obtained by allowing it to stand overnight. When the film thickness was measured by ellipsometry, it was 100 nm.

(Creation of graft pattern A (acrylic acid graft pattern))
The grafted silicon substrate A is brought into close contact with a mask pattern (NC-1, manufactured by Toppan Printing Co., Ltd.) formed on a quartz plate, and using a UV exposure machine (Ushio Electric Co., Ltd., UVL-4001-N, high-pressure mercury lamp). Irradiated for 20 minutes. Then, it wash | cleaned with the pure water and the graft pattern A was obtained.

(Check pattern)
The graft pattern A was observed with an atomic microscope AFM (Nanopics 1000, manufactured by Seiko Instruments Inc., using a DFM cantilever). As a result, it was confirmed that a pattern in which a line width of 8 μm and a gap width of 8 μm exist alternately was formed.

(Formation of metal (fine particle) film)
The obtained graft pattern A was immersed in a 15% by mass aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 12 hours and then washed with distilled water. Thereafter, the pattern A was immersed in 100 ml of distilled water, and 30 ml of 0.2M sodium tetrahydroborate was dropped into the distilled water to reduce the adsorbed silver ions. A uniform Ag metal film (metal (fine particle) film) was formed on the surface of the portion where the metal exists. The formed Ag metal film had a thickness of 0.1 μm. Thus, a metal (fine particle) film pattern material A-1 on which an Ag (fine particle) film was formed was obtained.

[Evaluation of conductivity]
When the surface conductivity of the pattern portion of the obtained Ag (fine particle) film was measured by the four-probe method using LORESTA-FP (manufactured by Mitsubishi Chemical Corporation), it showed 100Ω / □.

[Evaluation of metal thin film]
1. Film strength (adhesion)
The metal (fine particle) film pattern material A-1 on which an Ag (fine particle) film was formed was evaluated for film adhesion by a cross-cut tape method in accordance with JIS 5400. When the tape was peeled off from the cut grid, the first peel was not observed, and it was confirmed that the adhesion with the substrate was good.
2. Durability The surface of the metal (fine particle) film pattern material A-1 on which an Ag (fine particle) film was formed was rubbed back and forth 30 times by hand with a cloth (BEMCOT, manufactured by Asahi Kasei Kogyo Co., Ltd.) moistened with water. . When the surface was visually observed after rubbing, peeling of the metal (fine particle) film was not observed. Further, when the film adhesion was evaluated by the cross-cut tape method for the sample after rubbing in the same manner as described above, the first peeling was not observed, and the metal (fine particle) film adhered to the substrate even after rubbing. It was confirmed that the durability was not lowered and the durability was excellent.

[Example 2]
(Metal pattern formation)
Graft pattern A obtained in the same manner as in Example 1 was immersed in an aqueous solution of 0.1% by mass of palladium nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 hour, and then washed with distilled water. Then, it immersed in the electroless-plating bath of the following composition for 20 minutes, and produced metal pattern A-2.
<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 surface of the metal pattern A-2 was observed using an optical microscope (manufactured by Nikon, OPTI PHOTO-2), a good pattern in which a line width of 8 μm and a gap width of 8 μm existed alternately was confirmed.
[Evaluation of conductivity]
When the surface conductivity of the obtained Cu plating film pattern portion was measured by the same method as in Example 1, it was 50Ω / □.

[Evaluation of metal film]
1. Film strength (adhesion)
As described above, the film adhesion of the metal film pattern material A-2 on which the Cu film was formed was evaluated. When the tape was peeled off from the cut grid, the first peel was not observed, and it was confirmed that the adhesion with the substrate was good.

  The conductive pattern obtained by the present invention can form a fine pattern, has high conductivity, and the metal fine particle pattern material has a metal fine particle dispersion layer in which metal fine particles are dispersed at high density and has excellent durability. Since it can be formed into a desired fine pattern, it requires high electrical conductivity and any pattern formation, such as metal wiring materials and electromagnetic wave shields, for example, circuit formation including circuit formation such as micromachines and VLSI Application to CRT and plasma display, electromagnetic shielding filter, transparent electrode for display, light control device, solar cell, touch panel and other transparent conductive film, high density magnetic disk, magnetic head, magnetic tape, magnetic sheet, magnetic disk, etc. It can be applied to a wide range of uses such as magnetic materials.

Claims (7)

  A surface graft material having a graft polymer chain formed by covalent bonding directly at one end via a site that can be photocleavable is exposed to the substrate surface, and the photocleavable site is cleaved in the exposed region, After the graft polymer chain is removed to form the existence region / non-existence region of the graft polymer chain, a metal ion or a metal salt is added to the existence region of the graft polymer chain, and the metal ion or the metal ion in the metal salt Conductive pattern material formed by reducing metal to form a metal thin film. A surface graft material having a graft polymer chain formed by covalent bonding directly at one end via a site that can be photocleavable is exposed to the substrate surface, and the photocleavable site is cleaved in the exposed region, Removing the graft polymer chain to form an existing region / absent region of the graft polymer chain;
Applying a metal ion or a metal salt to a region where the formed graft polymer chain is present;
Reducing the metal ions or the metal ions in the metal salt to form a metal thin film;
A method for forming a conductive pattern.   3. The method according to claim 2, further comprising a heating step of heating the substrate on which the metal thin film is formed to 100 to 400 ° C. after the step of reducing the metal ion or the metal ion in the metal salt to form a metal thin film. The conductive pattern forming method.   A surface graft material having a graft polymer chain formed by covalent bonding directly at one end via a site that can be photocleavable is exposed to the substrate surface, and the photocleavable site is cleaved in the exposed region, After removing the graft polymer chain to form an existing region / absent region of the graft polymer chain, a metal ion or a metal salt is added to the existing region of the graft polymer chain, and the metal ion or the metal ion in the metal salt is added. A fine metal particle pattern material formed by reducing to form a fine metal particle adsorption region. A surface graft material having a graft polymer chain formed by covalent bonding directly at one end via a site that can be photocleavable is exposed to the substrate surface, and the photocleavable site is cleaved in the exposed region, Removing the graft polymer chain to form an existing region / absent region of the graft polymer chain;
Applying a metal ion or a metal salt to a region where the formed graft polymer chain is present;
Reducing the metal ions or the metal ions in the metal salt to precipitate metal fine particles, and forming a metal fine particle adsorption region;
A method for forming a fine metal particle pattern.   A surface graft having a graft polymer chain that has a functional group that interacts with the electroless plating catalyst or its precursor on the surface of the substrate and is directly bonded to one end through a covalent bond via a photocleavable site. After exposing the material, cleaving the photocleavable site in the exposed area, removing the graft polymer chain to form the existing area / absent area of the graft polymer chain, and then electrolessly in the existing area of the graft polymer chain A conductive pattern material formed by applying a plating catalyst or a precursor thereof and then performing electroless plating to form a metal thin film. A surface graft having a graft polymer chain that has a functional group that interacts with the electroless plating catalyst or its precursor on the surface of the substrate and is directly bonded to one end through a covalent bond via a photocleavable site. Exposing the material, cleaving the photocleavable site in the exposed area and removing the graft polymer chain to form an existing / absent area of the graft polymer chain;
Applying an electroless plating catalyst or a precursor thereof to an existing region of the formed graft polymer chain;
Forming a metal thin film by electroless plating;
A method for forming a conductive pattern.