WO2008038500A1

WO2008038500A1 - Laminate, method of forming conductive pattern, conductive pattern obtained thereby, printed wiring board, thin-layer transistor and apparatus utilizing these

Info

Publication number: WO2008038500A1
Application number: PCT/JP2007/067308
Authority: WO
Inventors: Yasuaki Matsushita; Hiroshi Sato
Original assignee: Fujifilm Corporation
Priority date: 2006-09-28
Filing date: 2007-09-05
Publication date: 2008-04-03

Abstract

A laminate comprising a glass substratum; a polymerization initiation layer of 0.1 to 100 μm thickness formed by chemical bonding, to the glass substratum, of a polymer having a radical polymerization initiation moiety and a moiety capable of direct chemical bonding to the glass substratum; and a graft polymer precursor layer containing a polymer having in its molecule a skeleton derived from a structure selected from among (meth)acrylic ester and (meth)acrylamide and having an unsaturated moiety capable of radical polymerization and a moiety capable of adsorbing an electroless plating catalyst. Further, there is provided a method of forming a conductive pattern with the use of the laminate.

Description

Specification

LAMINATE, CONDUCTIVE PATTERN FORMING METHOD AND CONDUCTIVE PATTERN OBTAINED BY THE METHOD, PRINTED WIRING BOARD AND THIN LAYER TRANSISTOR, AND DEVICE USING THEM

Technical field

[0001] The present invention relates to a laminate, a conductive pattern forming method and a conductive pattern using the laminate, a printed wiring board and a thin layer transistor provided with the conductive pattern, and using them. Relates to the device.

Background art

In the formation of electronic wiring such as a printed circuit board, there is an increasing demand for forming electrical wiring on a large area substrate. Fine wiring with high definition and excellent conductivity is generally formed by a vapor phase method such as a vacuum film formation method. However, with this method, it is difficult to form a metal film having a uniform film thickness and film quality over a wide area, and the formation of highly reliable wiring, electrodes and the like has been desired.

In addition, when a metal film is formed on a large-area panel by a vapor phase method, a huge vacuum film forming apparatus and ancillary equipment such as a gas supply facility are required, which causes a problem that enormous capital investment is required. .

In addition, vacuum deposition equipment such as sputtering equipment and CVD equipment requires a lot of power, such as power to drive the vacuum pump, power to heat the substrate, and power to generate plasma. Along with this, problems such as the increase in energy consumption of these manufacturing equipment also arise.

[0003] Further, when forming a metal wiring or the like, conventionally, after forming a metal film on the entire surface of the substrate using a vacuum film forming apparatus, an unnecessary portion is removed by etching, whereby an electrical wiring pattern is formed. Was forming. However, with this method, the resolution of the wiring is limited, and there is a problem when the waste of metal material occurs. In recent years, due to environmental considerations, reduction of energy consumption in manufacturing processes and effective use of material resources are required, and a method capable of forming a metal film pattern with a desired resolution more easily is required.

[0004] In contrast, for example, a catalyst layer necessary for an electroless plating reaction is preliminarily placed on a substrate. An electroless plating technique in which a metal film is selectively formed only in the region where the catalyst layer exists (see, for example, Patent Document 1), or a metal oxide film (eg, ZnO) is formed on the substrate surface. After the formation, a method has been proposed in which the metal oxide film is patterned and a metal film pattern is selectively formed on the formed metal oxide film pattern (see, for example, Patent Document 2). With these methods, the ability to form a metal wiring with a desired pattern In the former case, when a metal film pattern is formed on a substrate with a smooth surface such as a glass substrate by electroless bonding, the substrate and the plating film are in close contact with each other. However, it was difficult to increase the thickness of the plating film. In the latter case, the process of patterning the zinc oxide film formed on the entire surface of the substrate requires the use of a resist resin or the like, and the process is complicated and the chemical resistance of zinc oxide is low. Due to this, fine adjustment of the etching rate is required, and it is difficult to improve the in-plane uniformity of the etching rate on a large area substrate.

[0005] Further, as these improved technologies, a material serving as a catalyst is supported on a photosensitive film, a catalyst layer patterned by ultraviolet exposure is formed, and a zinc oxide film is formed only in that region, and this is used as a starting point. A method for forming a metal pattern by electroless plating has been proposed (for example, see Patent Document 3). This method has the advantage that a high-resolution zinc oxide film pattern is formed, but requires a special material such as a photosensitive film, and the formation of two catalyst layers before the formation of the metal film. The process was complicated, requiring 5 processes.

[0006] In response to this, the applicant of the present application has proposed a conductive pattern material capable of directly forming an image based on digital data by scanning a laser having a wavelength of 250 nm to 700 nm (for example, patents). (Ref. 4). However, with regard to the plating film that can be produced by this method, the formation of metal wiring by the full additive method that uses only the electroless plating method is a number from the viewpoint of conductivity and durability. Where the plating thickness is required, when the substrate is a glass substrate containing quartz glass, the surface of the substrate is eroded by alkali, which is often strongly alkaline during the electroless plating process. This causes a problem that the metal wiring part cannot be brought into close contact. It is possible to solve this problem by shortening the processing time. S When wiring is formed by the plating method, the processing time and the wiring film thickness are in a proportional relationship, and the electrical characteristics such as resistance value are Satisfied It is very difficult to form a wiring.

Patent Document 1: Japanese Patent Laid-Open No. 2000-147762

Patent Document 2: JP 2001-85358 Koyuki

Patent Document 3: Japanese Patent Laid-Open No. 2003-213436

Patent Document 4: Japanese Unexamined Patent Application Publication No. 2006-104045

Disclosure of the invention

Problems to be solved by the invention

[0007] Therefore, a conductive pattern forming method capable of forming a pattern having excellent adhesion to a substrate and good conductivity is desired. In addition, a laminate that can be used in the conductive pattern forming method is desired!

Means for solving the problem

[0008] As a result of the study, the present inventors have studied that a polymer having a thickness of 0 .; 1 m or more having a radical polymerization initiating ability on a glass substrate in the production of a conductive pattern or the like using graft polymerization. An initiating layer and a layer with a specific graft polymer precursor were formed to complete the present invention.

[0009] The first aspect of the present invention is formed by chemically bonding a glass substrate, a polymer having a radical polymerization initiation site and a site capable of being directly chemically bonded to the glass substrate, to the glass substrate. A polymerization initiating layer having a thickness of 0 · 11 to 100 m and a radical having a skeleton derived from a structure selected from (meth) acrylic acid ester and (meth) acrylic acid amide in the molecule Provided is a laminate having a polymer having a polymerizable unsaturated site and a site for adsorbing an electroless catalyst.

As a result, it is possible to obtain a laminate that can be used to form a conductive pattern that has excellent adhesion to the substrate and has good conductivity. The thickness of the polymerization initiating layer is preferably from 0.3 to 50 μm, preferably S, and more preferably from 0.5 to 10 μm.

[0010] The unsaturated site capable of radical polymerization is preferably a group selected from a (meth) atalyloylmethyl group. Here, the (meth) atalyloylmethyl group means an atalyloylmethyl group, a (meth) atalyloylmethyl group, or both.

Further, the weight average molecular weight of the polymer having the radical polymerization initiation site and the site capable of being directly chemically bonded to the glass substrate is not particularly limited. From the standpoint of fabric suitability, force, etc. 1000-; preferably 1000000 <, 3000-; more than 100,000; <5000-50,000 are particularly preferred. By setting the weight average molecular weight of the positive mer to 1000 to 1000 000, a polymer solution can be easily prepared, and the coated surface is good, which is preferable.

[0011] Furthermore, the glass substrate and the polymer are chemically bonded to each other by being a site force capable of being directly chemically bonded to the glass substrate, such as a halosilyl group, an alkoxysilyl group, a cyclic ether group, or an isocyanate group. This is preferable. Furthermore, it is preferable that the glass base material is mainly composed of a silicon oxide.

[0012] In a second aspect of the present invention, energy is applied in a pattern on the laminate, and radicals are generated at radical polymerization initiation sites of the polymer in the polymerization initiation layer of the laminate, A step of generating a graft polymer starting from a radical, and a step of adsorbing an electroless catalyst or a precursor thereof to the generated graft polymer, followed by electroless plating to form a conductive film, A conductive pattern forming method is provided.

In addition, it is a preferable aspect to further include an electroplating treatment step after the step of forming the conductive film.

[0013] A third aspect of the present invention provides a conductive pattern formed using the conductive pattern forming method provided by the second aspect.

The fourth aspect of the present invention provides a printed wiring board provided with the conductive pattern provided by the third aspect.

The fifth aspect of the present invention provides a thin film transistor having the conductive pattern provided by the third aspect.

According to a sixth aspect of the present invention, there is provided an apparatus comprising the printed wiring board provided by the fourth aspect.

The seventh aspect of the present invention provides a device comprising the thin film transistor provided by the fifth aspect.

The invention's effect

[0014] According to the present invention, a pattern having excellent conductivity with a substrate and good conductivity is obtained. It is possible to provide a method for forming a conductive pattern that can be formed, and a conductive pattern obtained thereby.

In addition, according to the present invention, it is possible to provide a laminate that can be used in the conductive pattern forming method.

Furthermore, according to the present invention, there is provided a printed wiring board or a thin layer transistor, and a printed wiring board or a thin layer transistor having a conductive film excellent in adhesion with a base material and having a good film thickness. An apparatus can be provided.

Brief Description of Drawings

FIG. 1 is a conceptual diagram showing an outline of a photocleavable compound bonding process strength graph polymer production process in the conductive pattern forming method of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The laminate of the present invention is formed by a glass substrate; a polymer having a radical polymerization initiation site and a site that can be directly chemically bonded to the glass substrate, which is formed by chemical bonding to the glass substrate. m to 100 m polymerization initiating layer; a skeleton derived from a structure selected from (meth) acrylic acid ester and (meth) acrylic acid amide in the molecule, and radically polymerizable unsaturated sites and electroless And a graft polymer precursor layer comprising a polymer having a site for adsorbing a catalyst.

[0017] The laminate of the present invention having the above-described configuration can be used in a conductive pattern forming method that is excellent in adhesion to a substrate and can form a good conductive pattern.

[0018] The "conductive pattern" in the present invention can be confirmed by observing with an atomic microscope (AFM) or an electron microscope (SEM).

[0019] 1. Laminate

(Polymerization initiation layer)

The polymerization initiation layer in the present invention has a thickness of 0.1 am or more and 100 μm formed by a polymer having a radical polymerization initiation site and a site that can be directly chemically bonded to the glass substrate chemically bonded to the glass substrate. It is a layer of m or less.

[0020] It has a radical polymerization initiation site and a site capable of direct chemical bonding with a glass substrate. When the polymer to be bonded is chemically bonded to the glass substrate, the adhesion between the substrate and the polymerization initiating layer can be improved. Moreover, alkali resistance can be imparted to the glass substrate by setting the thickness of the formed polymerization initiation layer to 0.1 m or more and 100 m or less.

[0021] The thickness of the polymerization initiating layer needs to be 0.1 am or more and 100 μm or less. From the viewpoint of preventing alkali from approaching the glass substrate surface, it is preferably from 0 · 3 m to 50 m, more preferably from 0.5 · 11 to 10 m. When the thickness of the polymerization initiating layer is in the range of from 0.3 m to 50 m, the alkali resistance effect tends to increase. The polymerization initiating layer having such a thickness becomes a rigid layer by using a polymer described later.

Next, the components of the polymerization initiation layer will be described.

[0022] (Polymer having radical polymerization initiation site and site capable of direct chemical bonding to glass substrate)

The polymer forming the polymerization initiating layer is a polymer having a radical polymerization initiating site and a site that can be directly chemically bonded to the glass substrate. Examples of the polymer include a site capable of directly chemically bonding to a glass substrate (hereinafter also simply referred to as a substrate binding site) and a polymerization initiation site capable of initiating radical polymerization by photocleavage (hereinafter simply referred to as polymerization initiation). It is preferably a compound having a portion.

[0023] Hereinafter, it has a polymerization initiation site (polymerization initiation site (Y)) capable of initiating radical polymerization by photocleavage, and a site (substrate binding site (Q)) capable of directly chemically bonding to the glass substrate. The structure of the polymer will be specifically described.

[0024] For this polymer, the base material binding site (Q) and the polymerization initiation site in the conceptual diagram of FIG.

This is described in detail using a model of the compound (Q Y) having (Y).

[0025] The polymerization initiation site (Y) is a structure containing a single bond that can be cleaved by light. Single bonds that are cleaved by light include carbonyl α-cleavage, zero-cleavage reaction, light-free rearrangement reaction, phenacyl ester cleavage reaction, sulfonimide cleavage reaction, sulfonyl ester cleavage reaction, ヒドロキシ hydroxysulfonyl ester cleavage reaction, benzylimide cleavage Examples thereof include a single bond that can be cleaved using a reaction, a cleavage reaction of an active halogen compound, or the like. These reactions break a single bond that can be cleaved by light. This cleavable single bond includes C-C bond, C C bond, C Ο bond, C C1 bond, Ν Ο bond, and S- — bond. I can get lost.

[0026] The polymerization initiation site (Y) containing a single bond that can be cleaved by light serves as a starting point for graft polymerization in the graft polymer formation step. Therefore, when a single bond that can be cleaved by light is cleaved, radical cleavage occurs due to the cleavage reaction. It has the function to generate.

As described above, the structure of the polymerization initiation site (Υ) having a single bond that can be cleaved by light and capable of generating radicals includes an aromatic ketone group, a phenacyl ester group, a sulfonimide group, and a sulfonyl ester. And a structure containing a group such as a group, Ν-hydroxysulfonyl ester group, benzylimide group, trichloromethyl group, benzyl chloride group.

[0027] Since the polymerization initiation site (Υ) is cleaved by exposure to generate a radical, if there is a polymerizable compound in the vicinity of the radical canole, this radical functions as a starting point for the graft polymerization reaction. The graft polymer can be produced (graft polymer production region).

[0028] On the other hand, the force at which the polymerization initiation site (され) is not exposed to light, the cleavage of the polymerization initiation site (Υ) does not occur in the region, and no graft polymer is formed in the region (graft). Polymer non-production region).

On the other hand, the base material binding site (Q) is composed of a reactive group capable of reacting with and binding to a functional group (基) present on the surface of the glass base material. Examples of the reactive group include a halosilyl group (preferably a chlorosilyl group, a dichloroalkylsilyl group, a chlorodialkylsilyl group, more preferably a chlorosilyl group and a dichloroalkylsilyl group), an alkoxysilyl group (preferably. , A C1-C2 alkoxysilyl group), a cyclic ether group (preferably a C2-C6 and oxygen number;! -2, more preferably a C2-C3 and oxygen-one cyclic ether) Group) or an isocyanate group.

As the alkyl group substituted on the silyl group, an alkyl group having 1 to 2 carbon atoms is preferred.

Specific examples of the base material binding site (Q) include the following groups, but are not limited thereto.

[0030] [Chemical 1] Q: Substrate binding site

— Si (OMe) ₃ — SiCI ₃ — NCO —CH ₂ CI — <^

[0031] 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. This 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.

[0032] Specific examples of the compound (Q-Y) having a substrate binding site (Q) and a polymerization initiation site (Υ) [Example Compound T1 to Example Compound Τ10] together with the cleavage portion are shown below. The present invention is not limited to these.

[0033] [Chemical 2]

0 \,

C-CI bond cleavage

C-CI bond cleavage

Cl ₃

[0034] [Chemical 3] T7

(n = 80, m = 20)

C-CI bond cleavage

The initiation layer is bonded onto the glass substrate through a chemically bondable site of the polymer. It is a layer. That is, as shown in FIG. 1, the polymerization initiating layer can be formed by bonding the compound (Q—Y) to the functional group (Z) present on the surface of the glass substrate. As a method of bonding the compound (Q—Y) to the functional group (Z) present on the surface of the glass substrate, the exemplified compound (Q—Y) is dissolved or dispersed in an appropriate solvent such as toluene, hexane, or acetone. Then, apply 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.

[0036] At this time, the concentration of the compound (Q—Y) in the solution or dispersion is preferably 0.01% by mass to 30% by mass, and 0.1% by mass to 15% by mass. Is particularly preferred. The liquid temperature when the solution or dispersion is brought into contact with the glass substrate is preferably 0 ° C to 100 ° C. The contact time is preferably 1 second to 50 hours, more preferably 10 seconds to 10 hours.

[0037] The polymer that forms the polymerization initiating layer can be synthesized with the force S by using the method described in Examples described later.

[0038] (Graft polymer precursor layer)

The graft polymer precursor layer has a skeleton derived from a structure selected from (meth) acrylic acid ester and (meth) acrylic acid amide in the molecule, and includes an unsaturated site capable of radical polymerization and an electroless plating catalyst. A polymer having a site to be adsorbed (hereinafter also simply referred to as “graft polymer precursor”).

Here, “(meth) acrylic acid ester and (meth) acrylic acid amide” mean acrylic acid ester, methacrylic acid ester, acrylic acid amide, and methacrylic acid amide.

[0040] The "skeleton derived from the structure selected from (meth) acrylic acid ester and (meth) acrylic acid amide" is selected from the skeletal forces represented by the following structural formulas (A) to (D) Means things. Hereinafter, it may be simply referred to as “skeleton”.

[0041] [Chemical 4]

[0042] In structural formulas (A) to (D), "*" represents a linking site between a skeleton represented by the structural formula and an atom adjacent thereto in the graft polymer precursor.

[0043] Examples of the unsaturated site capable of radical polymerization include polymerizable unsaturated groups (radical polymerizable groups). From the viewpoint of radical polymerizability, a (meth) atalyloylmethyl group is preferred.

[0044] The site that adsorbs the electroless plating catalyst includes a polar group, and the polar group is a hydrophilic group from the viewpoint of the adsorptivity (adhesiveness) of the electroless plating catalyst. Is preferred. Examples of the hydrophilic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, a hydroxyl group, an amide group, and an ether group.

[0045] The graft polymer precursor in the present invention is not particularly limited as long as it is a polymer having the skeleton and having an unsaturated site capable of radical polymerization in the molecule and a site adsorbing an electroless catalyst. Not. Among them, the hydrophilic group that is a polar group is preferable as the site that adsorbs the electroless plating catalyst. Therefore, the graft polymer precursor may be a hydrophilic polymer having a polymerizable unsaturated group, a hydrophilic macromer, or the like. And what has the said frame | skeleton is preferable.

[0046] Hereinafter, the synthesis of a hydrophilic polymer having a polymerizable unsaturated group and a hydrophilic macromer will be described.

[0047] One hydrophilic polymer having a monopolymerizable unsaturated group

A hydrophilic polymer having a polymerizable unsaturated group is a radically polymerizable group-containing hydrophilic polymer in which an ethylene addition polymerizable unsaturated group such as a bur group, a aryl group, or a (meth) taroloyl group is introduced in the molecule. Point to. This radically polymerizable group-containing hydrophilic polymer preferably has a polymerizable group at the end of the main chain or at the side chain, and has a polymerizable group on both sides. Is more preferable.

[0048] Such a radically polymerizable group-containing hydrophilic polymer can be synthesized as follows.

As a synthesis method, a method of copolymerizing a ω hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group, (b) copolymerizing a hydrophilic monomer and a monomer having a double bond precursor, And (C) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group. Among these, from the viewpoint of synthesis suitability, (C) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group is particularly preferable.

[0049] In the above methods (a) and (b), the hydrophilic monomer used in the synthesis of the radical polymerizable group-containing hydrophilic polymer may be (meth) acrylic acid or an alkali metal salt thereof. Biamine salt, itaconic acid or its alkali metal salt and amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N monomethylol (meth) acrylamide, N dimethylol (meth) acrylamide, arylamine or halogenated thereof Hydrogenate, 3 bupropionic acid or its alkali metal salt and amine salt, vinyl sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-Acrylamide-2-methylpropanosulfonic acid, reed Hydrophilic groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups or their salts, hydroxyl groups, amide groups and ether groups, such as phosphophosphooxypolyoxyethylene glycol mono (meth) acrylate. The monomer which has is mentioned.

[0050] As the hydrophilic polymer used in the method (c), a hydrophilic homopolymer or copolymer obtained by using at least one selected from these hydrophilic monomers is used.

[0051] When the radically polymerizable group-containing hydrophilic polymer is synthesized by the method (a), examples of the monomer having an ethylene addition polymerizable unsaturated group that is copolymerized with the hydrophilic monomer include an aryl group-containing monomer. Specific examples include araryl (meth) acrylate and 2-aryloxy cetyl methacrylate. [0052] In addition, when synthesizing a radically polymerizable group-containing hydrophilic polymer by the method (b), a monomer having a double bond precursor that is copolymerized with a hydrophilic monomer is 2- (3-chloro-1).

[0053] Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (c), a carboxyl group, an amino group or a salt thereof in the hydrophilic polymer, and a functional group such as a hydroxyl group and an epoxy group It is preferable to introduce an unsaturated group using the reaction of. Examples of the monomer having an addition polymerizable unsaturated group used for this purpose include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isocyanatoethyl (meth) acrylate. It is done.

[0054] One hydrophilic macromonomer

The method for producing a macromonomer that can be used in the present invention is described in, for example, Chapter 2 of “Macromonomer Chemistry and Industry” (Editor, Yuya Yamashita) published on September 20, 1999, published by IPC Publishing Bureau. Various production methods have been proposed in “Synthesis”!

Particularly useful hydrophilic macromonomers that can be used in the present invention include macromonomers derived from carboxy group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropane sulfonic acid, and vinylsterene. Sulfonic acid-based macromonomers derived from monomers of sulfonic acid and its salts, amide-based macromonomers derived from (meth) acrylamide, N-Bulucetamide, N-Buluformamide, N-Bulucarboxylic acid amide monomers , Macromonomers derived from hydroxyl group-containing monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxy ethynoleate acrylate, methoxy polyethylene glycolate acrylate, polyethylene Alkoxy or Echirenokishido group-containing monomer force, such as glycol Atari rate also macromonomers derived. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be used effectively as the macromonomer of the present invention.

Of these hydrophilic macromonomers, useful ones have a molecular weight in the range of 250 to 100,000, with a particularly preferred range of 400 to 30,000.

[0055] The graft polymer precursor in the present invention specifically has the polymerizable unsaturated group. Using the hydrophilic polymer and the hydrophilic macromer to be synthesized, they can be synthesized by the method described in the Examples below.

[0056] As a method of forming the graft polymer precursor layer on the polymerization initiation layer, a method in which a solution or dispersion in which the graft polymer precursor is dissolved is applied, or the polymerization initiation layer is applied to the solution or dispersion. There is a method of immersing the base material on which is formed.

[0057] At this time, the concentration of the graft polymer precursor in the solution or in the dispersion is 0.1% by mass.

˜50% by mass is preferred, especially 1% by mass˜; preferably 10% by mass.

[0058] Specific examples of graft polymer precursors are shown below. The present invention is not limited to these.

[0059] [Chemical 5]

: Weight average molecular weight: 27000)

: Weight average molecular weight: 31000)

Solvent

The solvent for dissolving and dispersing the above-mentioned graft polymer precursor is not particularly limited as long as the compound and additives added as necessary can be dissolved. For example, in the case where a hydrophilic compound is applied as the graft polymer precursor, a mixture of water or an aqueous solvent such as a water-soluble solvent is preferred, or a surfactant is further added to the solvent. Is preferred. The water-soluble solvent refers to a solvent miscible with water at an arbitrary ratio. Examples of such water-soluble solvents include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerin, and acetic acid. Examples thereof include acids, ketone solvents such as acetone, amide solvents such as formamide, and the like.

[0061] Graft The thickness of the polymer precursor layer is not particularly limited, 0.3 ^ 111-5 ^ 111 Ca from the viewpoint of metal adsorbing the plating catalyst, 0.5 ^ ^111-2 ^ 111 Kayori I like it. By setting the thickness of the graft polymer precursor layer in the range of 0.3 μm to 5 μm, the metal adsorption amount of the plating catalyst tends to increase, which is preferable.

[0062] (Glass substrate)

As the glass substrate used in the present invention, a glass substrate having a functional group (Z) such as a hydroxyl group, a carboxyl group, or an amino group can be applied to the surface of the substrate that is not particularly limited. There are no particular restrictions on the component, but it is preferable that the main component is silicon oxide from the viewpoint of easy chemical modification.

[0063] For chemical modification, using a silane coupling agent (a compound having an alkoxysilyl group or a halosilyl group at one end and a specific functional group at the other end) simplifies the process. And a surface coating is effective and desirable. At this time, amino groups, hydroxyl groups, mercapto groups, carboxyl groups, epoxy groups, and isocyanate groups are desirable as specific functional groups, among which amino groups, carboxyl groups, and groups having high reactivity with radical polymerization initiators. Isocyanate groups are preferred.

[0064] Specific examples of the silane coupling agent are not particularly limited as long as the silane coupling agent has the above-described configuration. 3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltri Ethoxysilane, 11-aminoundecyltriethoxysilane, 3-aminopropylmethyljetoxysilane, 3 aminopropyldimethylethoxysilane, N— (2 —aminoethyl) 3 aminopropyltrimethoxysilane, N— (2 Aminoethyl) -3-aminopropyltriethoxysilane, N— (2 aminoethyl) 3 aminopropylmethyldi Methoxysilane, (3-Trimethoxysilylpropyl) diethylenetriamine, 3-Mercaptopropyl pyrtriethoxysilane, 3-Mercaptopropyl trimethoxysilane, 11 Mercaptopyrmethyldimethoxysilane, 3-Isocyanatopropyltriethoxysilane, 3-Iso

2- (3,4 Epoxycyclohexenole) ethinoretriethoxysilane, 2- (3,4 Epoxy cyclohexyl) ethyltrimethoxysilane, (3-Glycidylpropyl) triethoxysilane, (3-Glycidinorepro Pinole) Trimethoxysilane, 5, 6-Epoxyhexenoletriethoxycinolesine methoxysilane, (3-Glycidinorepropinole) Dimethinoleethoxysilane, N (Trimethoxysilylpropyl) ethylenediamin sodium triacetate, 3- ( Triethoxysilyl) propyl succinic anhydride, etc., from the viewpoint of high reactivity with the radical polymerization initiator,

3-Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 4-Aminobutyltriethoxysilane, 3-Aminopropyldimethylethoxysilane, N— (2 Aminoethyl) 3-Aminopropyltrimethoxysilane, 3-Isocyanatopropyltriethoxy succinic anhydride is preferred.

[0065] In general, the force with which a flat glass substrate is used is not necessarily limited to a flat glass substrate, and a glass substrate having an arbitrary shape such as a cylindrical shape may be used. it can. Graft polymers can be introduced into these glass substrates.

[0066] Specific examples of the substrate suitable for the present invention include various glass substrates having a hydroxyl group on the surface, and various glass substrates having a surface modified with the specific functional group. .

The thickness of the glass substrate is selected according to the purpose of use and is not particularly limited, but is generally about 10 111 to 10 «11.

[0067] 2. Method of forming conductive pattern

In the conductive pattern forming method of the present invention, a radical polymerization initiation part of a polymer in a polymerization initiation layer of the laminate is provided by applying energy in a pattern on the laminate. A radical is generated at the position, and a graft polymer is generated starting from the radical (hereinafter, also referred to as “graft polymer generation process”), and an electroless plating catalyst or its catalyst is formed on the graft polymer formed in the pattern. And a step of forming a conductive film (hereinafter also referred to as a “conductive film forming step”) by performing electroless plating after adsorbing the precursor.

[0068] By using this method, a desired conductive pattern can be formed on the substrate, and in particular, an ultrafine conductive pattern can be formed. In addition, in the formation of the conductive pattern, the use of the laminate can remarkably improve the adhesion between the conductive film and the substrate and the resistance to alkalinity in the electroless plating bath of a useful draft polymer. Can

[0069] Here, "ultrafine" in the present invention means at least the width of the conductive film (conductive pattern) not exceeding SlOOOnm, and preferably the line and space width is 10 nm to 1000 nm, respectively. More preferably, the line and space widths are each in the range of lOnm to 500 nm.

The “ultrafine conductive pattern” in the present invention can be confirmed by observing with an atomic microscope (AFM) or an electron microscope (SEM).

[0070] Hereinafter, the graft polymer generation step and the conductive film formation step in the conductive pattern formation method of the present invention will be described in detail.

[0071] (Graft polymer production step)

In the graft polymer generating step in the conductive pattern forming method of the present invention, energy is imparted to the laminate in a pattern (pattern exposure), and the radical generated at the radical polymerization initiation site of the polymer in the polymerization initiation layer is the starting point. A graft polymerization reaction takes place and proceeds with the graft polymer precursor, and as a result, a graft polymer is formed only in the exposed area.

[0072] In the present invention, since the specific polymer is used as the graft polymer precursor, a thick and strong graft film can be formed.

[0073] In the graft polymer generation step, the exposure method that can be used for the pattern exposure is not particularly limited as long as the exposure can give energy with no limitation. Light is enough. Especially, from the viewpoint of forming a finer graft pattern, the visible region (360

Laser scanning exposure having a maximum absorption wavelength (up to 700 nm) or exposure including an ultraviolet region with a mercury lamp or the like and pattern exposure using a photomask are preferred.

[0074] The maximum absorption wavelength of the laser scanning exposure is preferably 360 nm to 550 nm, more preferably 365 nm to 450 nm.

[0075] Further, as the exposure energy, lOOOmj / cm ² or less It is preferable 500 mj / cm ² or less and more preferably more preferably fixture 300 mj / cm ² or less.

[0076] Examples of light sources used for exposure include ultraviolet light, deep ultraviolet light, and laser light. Specifically, excimer lasers such as ultraviolet light, i-line, g-line, KrF, and ArF are used. . Of these, i-line, g-line, and excimer laser are preferable.

[0077] The graft polymer precursor in the conductive pattern forming method of the present invention is the same as the graft polymer precursor contained in the laminate, and preferred examples are also the same.

Yes

[0078] The resolution of the graft pattern formed by the graft polymer production step in the present invention depends on the exposure conditions in the pattern exposure.

According to the graft polymer generation step of the present invention, an ultrafine graft polymer pattern can be formed, and a high-definition graft polymer pattern corresponding to the exposure is formed by performing high-definition pattern exposure. As described above, the exposure method for forming a high-definition graft polymer pattern includes light beam scanning exposure using an optical system, exposure using a mask, and the like. Take it.

In particular, pattern exposure when forming an ultra-fine graft polymer pattern with a line-and-space line width of lOOOnm or less includes the i-line stepper, g-line stepper, KrF stepper, and ArF stepper. Such stepper exposure, and exposure with a two-beam interference exposure machine.

[0079] Thus, in the graft polymer production step of the present invention, the substrate on which the graft polymer production region and the non-production region are formed on the surface of the glass substrate is subjected to treatment such as solvent immersion after exposure, Remove and purify the remaining graft polymer precursor and homopolymer The Specifically, washing with water or acetone, drying and the like can be mentioned. From the viewpoint of removal of the graft polymer precursor and homopolymer, it is preferable to use ultrasonic means. In the purified substrate, the graft polymer precursor and homopolymer remaining on the surface are completely removed, and only the patterned graft polymer firmly bonded to the substrate exists.

[0080] By passing through the graft polymer production step in the present invention, a fine pattern corresponding to the resolution of exposure can be easily formed, so the application range is wide.

The graft polymer pattern obtained by the method of the graft polymer production step in the present invention can be applied to, for example, a fine processing resist.

[0081] (Conductive film forming step)

Next, a process of forming a conductive film (conductive film forming process) in the conductive pattern forming method of the present invention will be described.

In this step, an electroless plating catalyst or a precursor thereof is adsorbed on the resulting graft polymer, and then electroless plating is performed to form a conductive film (hereinafter also simply referred to as “plating film”). Process.

[0082] (Formation of plating film)

The conductive film forming step is a method for forming a plating film by performing electroless plating after adsorbing an electroless plating catalyst or a precursor thereof to a polar group of the graft polymer. By this method, a conductive film made of a plating film is formed.

In this way, the plating film is formed by electroless attachment to the catalyst or precursor adsorbed on the polar group of the graft polymer, so that the plating film and the graft polymer are firmly bonded. As a result, the adhesion between the substrate and the adhesive film is excellent, and the conductivity can be adjusted according to the plating conditions.

First, a method for applying an electroless plating catalyst or a precursor thereof will be described.

The electroless plating catalyst used in the present invention 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 preferred because of their good handleability and high catalytic ability. As a method for fixing the zero-valent metal to the interactive region, for example, the charge is adjusted so as to interact with the polar group of the graft polymer. A method of applying the colloidal metal colloid to the base material on which the graft polymer is formed is used. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here, and the metal colloid whose charge is adjusted in this way interacts with the polar group of the graft polymer. Metal colloid (electroless plating catalyst) can be attached to the graft polymer.

[0084] The electroless plating catalyst precursor used in the present invention can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. The metal ions of the zero-valent metal used in the above electroless plating catalyst are mainly used. Electroless plating catalyst The metal ion that is a precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. After the metal ion, which is an electroless plating catalyst precursor, is applied to the base material on which the graft polymer is formed, it is converted into a zero-valent metal by a separate reduction reaction before immersion in the electroless plating bath. It can also be used as a catalyst! /, Immersed in an electroless plating bath as an electroless plating catalyst precursor, and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath. Good.

[0085] In practice, the metal ion that is an electroless plating catalyst precursor is imparted to the graft polymer in the form of a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion). M (NO) n, MCln,

Three

M (SO), M (PO) (M represents an n-valent metal atom), and the like. Metal

2 / n 4 3 / n 4

As on, those obtained by dissociating the above metal salts can be preferably used. Specific examples include Ag ion, Cu ion, A1 ion, Ni ion, Co ion, Fe ion, and Pd ion, and Ag ion and Pd ion are preferable in terms of catalytic ability.

[0086] As a method for applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating catalyst precursor to a graft polymer, the metal colloid is dispersed in a suitable dispersion medium, or a metal Prepare a solution containing the dissociated metal ions by dissolving the salt in an appropriate solvent, and apply the solution to the substrate on which the graft polymer is formed, or the substrate on which the graft polymer is formed in the solution Soak it. Contact solution containing metal ions By doing so, metal ions can be attached to polar groups of the graft polymer using ion ion interaction or dipolar ion interaction, or the interaction region can be impregnated with metal ions. . From the viewpoint of sufficiently performing such adhesion or impregnation, the metal ion concentration or the metal salt concentration in the contacted solution is preferably in the range of 0.0; More preferably, it is in the range of! -30 mass%. The contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour.

[0087] Next, an electroless plating method will be described.

By performing electroless plating on the substrate to which the electroless plating catalyst or its precursor is applied, a conductive film corresponding to the graft polymer generation region is formed.

Electroless plating refers to the operation of depositing metal by chemical reaction using a solution in which the metal ions to be deposited as a plating solution are dissolved.

[0088] The electroless plating in this step is performed, for example, by washing the substrate provided with the electroless plating catalyst with water to remove excess electroless plating catalyst (metal), and then electroless plating bath. Immerse in As the electroless bath used, a generally known electroless bath can be used.

[0089] Further, in the case of a substrate provided with an electroless plating catalyst precursor, that is, a substrate in a state where the electroless plating catalyst precursor adheres to or is impregnated with the graft polymer is used as an electroless plating bath. In the case of immersion, the substrate is washed with water to remove excess precursor (metal salt, etc.) and then immersed in an electroless plating bath. In this case, in the electroless plating bath, the precursor is reduced and subsequently electroless plating is performed. As the electroless bath used here, a generally known electroless bath can be used as described above.

[0090] The composition of a general electroless plating bath mainly includes 1. metal ions for plating, 2. reducing agents, 3. additives that improve the stability of metal ions (stabilizers). ing. In addition to these, this plating bath may contain known additives such as a plating bath stabilizer.

Yes

Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in electroless plating baths, and copper and gold are particularly preferred from the viewpoint of conductivity. That's right.

[0091] Further, there are optimum reducing agents and additives in accordance with the above metals. For example, a copper electroless bath has Cu (SO) as the copper salt, HCOH as the reducing agent, and copper ion as the additive.

4 2

Chelating agents such as EDTA and Rossiel salt are included. In addition, the bath used for electroless plating of CoNiP includes cobalt sulfate, nickel sulfate as the metal salt, sodium hypophosphite as the reducing agent, sodium malonate as the complexing agent, and sodium malate. Contains sodium succinate. In addition, the electroless plating bath of noradium is (Pd (NH)) C1 as a metal ion and ED as NH as a reducing agent.

3 4 2 3, H NNH, stabilizer

twenty two

TA is included. These plating baths may contain components other than the above components.

[0092] The thickness of the conductive film thus formed can be controlled by the concentration of the metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, or the like. From the viewpoint of conductivity, 0.5 m or more is preferable, and 3 m or more is preferable. In addition, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.

[0093] The conductive film obtained as described above has finely dispersed fine particles of electroless plating catalyst and plating metal in the graft polymer film by cross-sectional observation by SEM. It was confirmed that relatively large particles were deposited! Since the interface is a hybrid state of the graft polymer and fine particles, even if the average roughness (Rz) of the substrate surface is 3 m or less, the substrate (organic component) and the inorganic substance (electroless plating catalyst or plating) Adhesion with (metal) was good.

[0094] (Electric plating process)

In addition, it is preferable to have an electroplating treatment step after completion of electroless plating in the conductive film forming step. That is, electroplating is performed using the conductive film obtained by electroless plating as described above as an electrode. As a result, it is possible to easily form a new plating film having an arbitrary thickness on the basis of the conductive film having excellent adhesion to the substrate. By adding this step, the plating film can be formed to a thickness according to the purpose.

[0095] As a method of electroplating in the present invention, a conventionally known method can be used. . Examples of metals used for electrical plating include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferred. More preferred.

[0096] The thickness of the plating film obtained by electroplating varies depending on the application, and can be adjusted by adjusting the concentration of metal contained in the plating bath, the immersion time, or the current density. The power to roll up with S.

[0097] As described above, a conductive pattern having excellent adhesion to a substrate and having an ultrafine conductive film (plating film) is formed on a glass substrate by the method for forming a conductive pattern of the present invention. The forming force S is used.

[0098] 3. Conductive pattern

The conductive pattern of the present invention is formed by using the conductive pattern forming method described above, and various kinds of fine wiring that requires fine and excellent conductivity, such as a printed wiring board and a thin layer transistor. It can be applied to any use.

[0099] 4. Printed circuit board

The printed wiring board of the present invention is characterized by comprising a conductive pattern formed using the above-described conductive pattern forming method. By providing the conductive pattern formed on the printed wiring board using the conductive pattern forming method, the fine wiring with high definition and excellent conductivity is made uniform over a wide area with a uniform film thickness and film quality. be able to. Thereby, it can be set as the printed wiring board which has wiring with high reliability and an electrode.

[0100] The fine wiring with high definition and excellent conductivity obtained by the present invention can form a metal film having a uniform film thickness and film quality over a wide area as compared with the conventional vacuum film-forming method. It is possible to use highly reliable wiring and electrodes. In addition, it does not require huge capital investment, so it consumes less energy. The method using the vacuum film-forming apparatus is the ability to form an electric wiring pattern by forming a metal film on the entire surface of the substrate and then removing unnecessary portions by etching. In the present invention, the wiring resolution is limited. As a result, there is no waste of metal materials, so the burden on the environment is extremely low.

[0101] From the viewpoint of further improving the conductivity, the printed wiring board has the conductive pattern. It is preferable to provide a conductive film (conductive pattern) formed using a formation method and then to provide an electrical plating (metal plating) treatment step. As the metal plating, it is preferable that the metal plating is the same.

[0102] When the printed wiring board of the present invention is manufactured, the thickness of the plating film is preferably 0.3 m or more from the viewpoint of conductivity, more preferably 3 m or more. preferable.

[0103] 5. Thin layer transistor

The thin layer transistor of the present invention is characterized by having a conductive pattern formed by using the conductive pattern forming method described above.

More specifically, the thin film transistor of the present invention preferably has a gate electrode, a drain electrode, a source electrode, or a metal wiring, which is a conductive pattern formed by using the conductive pattern forming method. Masle.

[0105] By providing the conductive pattern formed using the conductive pattern forming method, the thin-layer transistor has a high-definition and highly conductive fine wiring over a wide area. The film quality can be formed uniformly. Thus, a thin layer transistor having highly reliable wiring and electrodes can be obtained.

[0106] 6. Equipment

The device of the present invention is characterized by comprising the printed circuit board or the thin layer transistor. Examples of such a device include a liquid crystal display device (LCD), a field emission display device (FED), an electrophoretic display device ( Flat panel displays such as EPD), plasma display (PDP), electochromic display (ECD), and electoluminescent display (ELD). By using the printed wiring board or the thin film transistor according to the present invention, the adhesiveness to the substrate is good at a desired resolution, and the device can be miniaturized and highly integrated.

[0107] The device of the present invention is not particularly limited except that it includes the printed wiring board or the thin-layer transistor, and can have known constituent elements. Among them, a display device is preferable. .

As described above, the gate electrode to which the conductive pattern obtained by the above of the present invention is applied, Liquid crystal display (LCD), field emission display (FED), electrophoretic display (EPD), plasma display (PDP), electochromic display (with drain electrode, source electrode or metal wiring) Flat panel displays such as ECD) and Electric Luminescent Display (ELD) can easily form electrodes and wiring with excellent resolution and adhesion to the substrate with the desired resolution. This is effective in all cases where a conductive layer is used to reduce the resistance of wiring such as display devices.

The preferred liquid crystal display device of the present invention is extremely useful when it is required to form electrodes or wiring by wet film formation instead of dry film formation, or when a large display area is required. is there. In addition, the active matrix display device suitable for the present invention can be applied not only to a flat panel display but also to a flat panel image sensor, and incorporates the thin layer transistor (also referred to as a TFT element) of the present invention. The active matrix substrate can be suitably used for various liquid crystal display devices.

Example

[0110] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0111] Synthesis Example 1: Polymerization initiation layer forming polymer T1

Irgacure 2959 (manufactured by Ciba Specialty Chemicals) 9 · OOg was dissolved in 30mL of THF, and 20mg of p-methoxyphenol, 6 · 28g of 2-methacryloyloxychetyl isocyanate, and 81mg of dibutyltin dilaurate were added. The reaction was performed at ° C for 4 hours. The solvent was removed under reduced pressure, and recrystallization was performed using ethyl hexane acetate to obtain a white solid.

Next, 10 g of this white solid was dissolved in 50 mL of methyl ethyl ketone, 15.7 g of glycidyl methacrylate and 140 mg of AIBN were added, and the mixture was heated to 70 ° C. and reacted for 6 hours. Thereafter, this solution was reprecipitated with hexane to obtain a polymerization initiation layer forming polymer T1.

The polymerization initiation layer-forming polymer T1 is the exemplified compound T1 given as a specific example of the compound (Q—Y).

[0112] Synthesis Example 2: Polymerization initiation layer forming polymer T2

2, 4-Bistrichloromethyl mono 6- (4-hydroxyphenyl) triazine 16. 4 g is dissolved in THF5 OmL, p-methoxyphenol 20 mg and 2-methacryloyloxychetyl isocyanate. 6.28 g of Nate and 81 mg of dibutyltin dilaurate were added and reacted at 50 ° C. for 4 hours. The solvent was removed under reduced pressure, and recrystallization was performed using ethyl hexane acetate to obtain a yellow solid. Next, 10 g of this yellow solid was dissolved in 168 mL of dimethylacetamide, 8.85 g of glycidyl methacrylate and 140 mg of AIBN were added, and the mixture was heated to 70 ° C. and reacted for 6 hours. Thereafter, this solution was reprecipitated with hexane to obtain a polymerization initiation layer forming polymer T2. The polymerization initiation layer forming polymer T2 is the exemplified compound T2 given as a specific example of the compound (Q—Y).

[0113] Synthesis Example 3: Hydrophilic polymer P1

18 g of polyacrylic acid (average molecular weight 25,000) was dissolved in 300 g of DMAc, 0.25 g of hydroquinone salt was added, and the mixture was reacted at 65 ° C. for 4 hours. The acid value of the obtained polymer was 7.02 meq / g. The carboxyl group was neutralized with IN sodium hydroxide aqueous solution, and the polymer was precipitated in addition to ethyl acetate and washed well to obtain hydrophilic polymer P1.

[0114] Synthesis Example 4: Hydrophilic polymer P2

18g of polyacryloleic acid (average molecular weight 25,000) was rapidly dissolved in DMAc300gi, 9.OOg of glycolenoleate and 22g of sodium bicarbonate were added, and reacted at 60 ° C for 8 hours. Then, neutralize with 1 N hydrochloric acid, and then add 0.41 g of hydroquinone, 21.2 g of 2-athaloyloxetyl isocyanate and 0.40 g of dibutinoretin dilaurate, 65. C, reacted for 4 days. This solution was added to ethyl acetate to precipitate the polymer, and washed well to obtain hydrophilic polymer P2.

[0115] Synthesis Example 5: Polymerization initiation layer forming polymer T7

Next, dissolve this white solid 10. Og in 35 mL of methyl ethyl ketone, add 1-64 g of 3- (trimethoxylinole) propinoremethacrylate, AIBN 65. Omg, and add 70. C was warmed for 6 days. Thereafter, this solution is reprecipitated with hexane to thereby form a polymerization initiating layer-forming layer. Obtained Rimmer T7.

The polymerization initiation layer-forming polymer Τ7 is the exemplified compound Τ7 given as a specific example of the compound (QΥ).

[0116] Synthesis Example 6: Polymer for forming polymerization initiation layer Τ8

Ν- [4- [4, 6 Bis (trichloromethyl) 1, 3, 5 triazine-2-yl] -4-hydroxybenzamide (Fuji Film Co., Ltd.) 40 · Og dissolved in 200 mL THF. Triethylamine 15. 8mL and 0.66mL of pyridine were added and cooled to 0 ° C in an ice bath. 12.3 g of methacrylic anhydride was added dropwise and stirred at room temperature for 12 hours, and then the solvent was removed under reduced pressure to obtain an oil. The oil was crystallized from hexane and washed with acetonitrile to give a yellow solid.

Next, 10 g of this yellow solid was dissolved in 62 · 2 mL of N, N dimethylacetamide, and 3- (trimethyloxylinole) propinoremethacrylate · 0 · 46 g and AIBN 115 mg were added. C was allowed to react for 6 hours at a warm temperature. Thereafter, 30 mL of THF was added to the reaction solution, followed by reprecipitation with hexane to obtain a polymerization initiation layer forming polymer T8.

The polymerization initiation layer forming polymer T8 is the exemplified compound T8 given as a specific example of the compound (QY).

[0117] Synthesis Example 7: Polymerization initiation layer forming polymer T9

Irgacure 2959 (Ciba Specialty Chemicals Co., Ltd.) 9000 g was dissolved in 30 mL of THF, 20 mg of p-methoxyphenol, 2 g of methacryloyloxychetyl isocyanate, 81 mg of dibutyltin dilaurate were added, and 50 ° C , Reacted for 4 hours. The solvent was removed under reduced pressure, and recrystallization was performed using ethyl hexane acetate to obtain a white solid.

Next, 10.0 g of this white solid was quickly dissolved in 132 mL of methinoretinoleketone, followed by power lens M OI (manufactured by Showa Denko) 8 · 18 g, benzenoremethacrylate 9 · 29 g, AIBN 287 mg. It was heated and heated to 70 ° C for 6 hours. Thereafter, this solution was reprecipitated with hexane to obtain a polymerization initiation layer forming polymer T9.

The polymerization initiation layer forming polymer T9 is the exemplified compound T9 given as a specific example of the compound (QY).

[0118] Synthesis Example 8: Polymerization initiation layer forming polymer T10

N- [4- [4, 6 Bis (trichloromethyl) 1, 3, 5 Triazine-2-yl] -4-hydride Roxybenzamide (Fuji Film) 40 · Og is dissolved in 200mL of THF. Add triethylenolemine (15.8 mL) and pyridine (0.60 mL) and cool to 0 ° C in an ice bath. 12.3 g of methacrylic anhydride was added dropwise and stirred at room temperature for 12 hours, and then the solvent was removed under reduced pressure to obtain an oil. This oil was crystallized from hexane and washed with acetonitrile to give a yellow solid.

Next, 10 g of this yellow solid was dissolved in 84 mL of N, N-dimethylacetamide, 7.17 g of glycidinomethacrylate, 2.96 g of benzenomethacrylate, and 179 mg of AIBN were added and heated to 70 ° C. The reaction was allowed to warm for 6 hours. Thereafter, 50 mL of THF was added to the reaction solution, and precipitation with hexane was performed to obtain a polymerization initiation layer forming polymer T10.

The polymerization initiation layer forming polymer T10 is the exemplified compound T10 given as a specific example of the compound (Q—Y).

[0119] Example 1

(Photocleavable compound binding process)

Surface cleaning was performed on a glass substrate (Nippon Sheet Glass) by UV ozone treatment for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.).

Next, the exemplified compound T1 a Te also溶力dehydrated E chill methyl ketone (2-butanone) was prepared 20 mass ^_0/0 solution, it was spin-coated on the substrate surface. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 170 ° C. for 1 hour and the surface was washed with ethyl methyl ketone. Then dried with an air gun, Exemplified Compound T1 was obtained a substrate A1 to have a polymerization initiating layer formed by bonding a glass substrate (polymerization initiation layer thickness: 5 - 0 ^ 111) ₀

[0120] (Graft polymer production process)

0.5 g of the hydrophilic polymer P1 obtained in Synthesis Example 3 above is dissolved in a mixed solvent of sodium hydrogen carbonate aqueous solution 4.62 g, dimethylacetamide (DMAc) O.05 g, and acetonitorinole 1.5 g to obtain a graft polymer precursor. A layer-forming coating solution was obtained.

The above coating solution for forming a graft polymer precursor layer was spin-coated on one surface of the substrate A1 obtained above. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. The substrate after applying the coating solution for forming the graft polymer precursor layer was dried at 80 ° C. for 5 minutes to form a graft polymer precursor layer. [0121] (Exposure)

The substrate Al after the formation of the graft polymer precursor layer was exposed in accordance with a predetermined pattern with an exposure machine (UNIKIURE UVX-02516 S 1LP01, manufactured by Usio Electric Co., Ltd.). After the exposure, the substrate surface was washed with water while gently rubbing with a wiper (Bencott, manufactured by Ozu Sangyo Co., Ltd.) and washed with Aceton for 7 fires.

As described above, a glass substrate B1 having a graft polymer layer formed in a pattern on the surface was formed.

[0122] The obtained pattern was observed with an atomic microscope AFM (Nanobix 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a pattern in which a line width of 10111 and a gap width of 10 m exist alternately was formed on the surface of the glass substrate B1.

[0123] (Conductive material layer forming process)

The obtained glass substrate B1 was immersed in a 1.0% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 minute, washed with water, and dried with an air gun. After that, electroless plating was performed by immersing in an electroless plating bath (pH: 12.4) having the following composition for 30 minutes. After electroless plating, it was washed with water and dried with an air gun.

Composition of electroless bath

300 g of water

Copper (II) sulfate pentahydrate 3.0 g

EDTA— 2Na dihydrate 8.9 g

Polyethylene glycol (average molecular weight 1000) 0.03g

2, 2'—Bibiridinole 0.3 mg

Ethylenediamine 0.12g

Sodium hydroxide 2.5g

Honolem Norede Dehydrated Water ί 夜（36. 0—38. 0%) 1. 6g

[0125] When this surface was observed with an electron microscope (Miniscope TM—1000 manufactured by HITACHI), a conductive pattern 1 with alternating line width of 10 m and gap width of 10 m was formed! / ヽ It was confirmed that

[0126] Example 2

(Photocleavable compound binding process)

Next, a 15% by mass solution of the exemplified compound 2 in dehydrated ethylmethylketone (2-butanone) was prepared, and this was spin coated on the substrate surface. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 170 ° C. for 1 hour, and the surface was washed with ethyl methyl ketone. Thereafter, it was dried with an air gun to obtain a substrate A2 having a polymerization initiating layer formed by binding Exemplified Compound T2 to a glass substrate (polymerization initiating layer thickness: 4.1 ^ 111) ₀

[0127] (Graft polymer production process)

0.5 g of the hydrophilic polymer P2 obtained in Synthesis Example 4 above is dissolved in a mixed solvent of sodium hydrogen carbonate aqueous solution 4.62 g, dimethylacetamide (DMAc) O. 05 g, and acetonitrile-1.5 g of graft polymer precursor. A layer-forming coating solution was obtained.

The above coating solution for forming a graft polymer precursor layer was spin-coated on one surface of the substrate A2 obtained above. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. Substrate A 2 after application of the coating solution for forming the graft polymer precursor layer was dried at 80 ° C. for 5 minutes to form a graft polymer precursor layer.

[0128] (Exposure)

The substrate A2 after the formation of the graft polymer precursor layer was exposed in accordance with a predetermined pattern using an exposure machine (UNIKIURE UVX-02516 S 1LP01, manufactured by Usio Electric Co., Ltd.). After the exposure, the substrate surface was washed with water while gently rubbing with a wiper (Bencott, manufactured by Ozu Sangyo Co., Ltd.) and washed with Aceton for 7 fires.

As described above, a glass substrate B2 having a graft polymer layer formed in a pattern on the surface was formed.

[0129] The obtained pattern was observed with AFM (Nanobix 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, the surface of glass substrate B2 has a line width of 10 m and is empty. It was confirmed that a pattern with alternating gap widths of 10 mm was formed.

[0130] (Conductive material layer formation process)

The obtained glass substrate B2 was immersed in a 1.0% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 minute, washed with water, and dried with an air gun.

Next, it was immersed in an electroless plating bath (commercial product) having the following composition for 30 minutes to perform electroless plating. After electroless plating, it was washed with water and dried with an air gun.

[0131] Composition of electroless bath

258g of water

ATS Ad Kappa IW— A 15mL

ATS Ad Kappa IW— M 24mL

ATS Ad Kappa IW— C 3mL

[0132] When this surface was observed with an electron microscope (Miniscope TM—1000 manufactured by HITACHI), it was confirmed that a conductive pattern 2 with alternating line width of 10 m and gap width of 10 m was formed! It was done.

[0133] Example 3

(Photocleavable compound binding process)

Surface cleaning was performed on a glass substrate (Nippon Sheet Glass) by UV ozone treatment for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.). The glass substrate was immersed in a 1% by mass aqueous solution of 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry) and allowed to stand for 10 minutes. The substrate was taken out, washed with distilled water and dried.

Next, the exemplified compounds T2 to prepare dehydrated E chill methyl ketone (2-butanone) 15 mass溶力also Te ^_0/0 solution, it was spin-coated on the substrate surface. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 170 ° C. for 1 hour and the surface was washed with ethyl methyl ketone. Thereafter, the substrate A3 was dried with an air gun to obtain a substrate A3 having a polymerization initiating layer formed by binding Exemplified Compound T2 to a glass substrate (polymerization initiating layer thickness: 4.1 m).

[0134] (Graft polymer production process) 0.5 g of the hydrophilic polymer P2 obtained in Synthesis Example 4 above is dissolved in a mixed solvent of sodium hydrogen carbonate aqueous solution 4.62 g, dimethylacetamide (DMAc) O. 05 g, and acetonitrile-1.5 g of graft polymer precursor. A layer-forming coating solution was obtained.

A coating solution for forming a graft polymer precursor layer was spin-coated on one surface of the substrate A3 obtained above. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. Substrate A3 after application of the coating solution for forming the graft polymer precursor layer was dried at 80 ° C. for 5 minutes to form a graft polymer precursor layer.

[0135] (Exposure)

As described above, a glass substrate B3 having a graft polymer layer formed in a pattern on the surface was formed.

[0136] The obtained pattern was observed with AFM (Nanobix 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a pattern having a line width of 10 m and a gap width of 10 mm was alternately formed on the surface of the glass substrate B3.

[0137] (Conductive material layer formation process)

The obtained glass substrate B3 was immersed in a 1.0% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 minute, washed with water, and dried with an air gun. Thereafter, electroless plating was performed by immersing in the electroless plating bath (pH: 12.4) described in Example 1 for 30 minutes. After electroless plating, it was washed with water and dried with an air gun.

[0138] When this surface was observed with an electron microscope (Miniscope TM—1000 manufactured by HITACHI), it was confirmed that a conductive pattern 3 having a line width of 10 m and a gap width of 10 m alternately formed was formed! It was done.

[0139] Example 4

(Photocleavable compound binding process) The surface of the glass substrate (Nippon Sheet Glass) was cleaned by UV ozone treatment for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.), and the substrate was washed with 3-aminopropyltrimethoxysilane 1 It was immersed in a mass% aqueous solution for 10 minutes, washed with water, and dried with an air gun.

Next, the exemplified compound T1 a Te also溶力dehydrated E chill methyl ketone (2-butanone) was prepared 20 mass ^_0/0 solution, it was spin-coated on the substrate surface. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 170 ° C. for 1 hour and the surface was washed with ethyl methyl ketone. Thereafter, the substrate A4 was dried with an air gun to obtain a substrate A4 having a polymerization initiating layer formed by binding Exemplified Compound T1 to a glass substrate (the thickness of the polymerization initiating layer: 5.0 m).

[0140] (Graft polymer production process)

0.5 g of the hydrophilic polymer P1 obtained in Synthesis Example 3 above is dissolved in a mixed solvent of sodium hydrogen carbonate aqueous solution 4.62 g, dimethylacetamide (DMAc) O. 05 g, and acetonitorinole 1.5 g to obtain a graft polymer precursor. A layer-forming coating solution was obtained.

The coating solution for graft formation layer was spin-coated on one surface of the substrate A4 obtained above. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. The substrate after the coating solution for forming the graft polymer precursor layer was applied was dried at 80 ° C. for 5 minutes to form a graft polymer precursor layer.

[0141] (Exposure)

The substrate A1 after the formation of the graft polymer precursor layer was exposed in accordance with a predetermined pattern with an exposure machine (UNIQURE UVX-02516 S 1LP01, manufactured by Usio Electric Co., Ltd.). After the exposure, the substrate surface was washed with water while gently rubbing with a wiper (Bencott, manufactured by Ozu Sangyo Co., Ltd.) and washed with Aceton for 7 fires.

As described above, a glass substrate B4 having a graft polymer forming layer formed in a pattern on the surface was formed.

[0142] The obtained pattern was observed with an atomic microscope AFM (Nanobix 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a pattern with alternating line width 10 111 and gap width 10 m was formed on the surface of glass substrate B4. It is.

[0143] (Conductive material layer forming process)

The obtained glass substrate B4 was immersed in a 1.0% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 minute, washed with water, and dried with an air gun. Thereafter, the electroless plating was carried out by immersing in a commercially available electroless plating bath described in Example 2 (ATS Adkappa, pH = 12.7, manufactured by Okuno Pharmaceutical Co., Ltd.) for 20 minutes. After electroless plating, it was washed with water and dried with an air gun.

[0144] When this surface was observed with an electron microscope (Miniscope TM—1000 manufactured by HITACHI), it was confirmed that a conductive pattern 4 having a line width of 10 m and a gap width of 10 m alternately formed! It was done.

[0145] Example 5

(Photocleavable compound binding process)

Next, the exemplified compounds T7 dehydration E chill methyl ketone (2-butanone) to be 20 mass ^_0/0 solution prepared Te溶力, it was spin-coated on the substrate surface. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 80 ° C. for 20 minutes, and the surface was washed with ethyl methyl ketone. Thereafter, the substrate A5 was dried with an air gun to obtain a substrate A5 having a polymerization initiation layer formed by binding Exemplified Compound T7 to a glass substrate (polymerization initiation layer thickness: 5.4 m).

[0146] (Graft polymer production process)

0.5 g of the hydrophilic polymer P1 obtained in Synthesis Example 3 above is dissolved in a mixed solvent of sodium hydrogen carbonate aqueous solution 4.62 g, dimethylacetamide (DMAc) O. 05 g, and acetonitorinole 1.5 g for the graft-forming layer. A coating solution was obtained.

The coating solution for forming the graft polymer precursor layer was spin-coated on one surface of the substrate A5 obtained above. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. The substrate after the coating solution for the graft polymer precursor layer forming layer was applied was dried at 80 ° C. for 5 minutes to form a graft polymer precursor layer. [0147] (Exposure)

The substrate A5 after the formation of the graft polymer precursor layer was exposed in accordance with a predetermined pattern with an exposure machine (UNIQURE UVX-02516 S 1LP01, manufactured by Usio Electric Co., Ltd.). After the exposure, the substrate surface was washed with water while gently rubbing with a wiper (Bencott, manufactured by Ozu Sangyo Co., Ltd.) and washed with Aceton for 7 fires.

As described above, a glass substrate B5 having a graft polymer layer formed in a pattern on the surface was formed.

The obtained pattern was observed with an atomic microscope AFM (Nanobix 1000, manufactured by Seiko Instruments Inc., using a DFM cantilever). As a result, it was confirmed that a pattern with alternating line width 10 111 and gap width 10 m was formed on the surface of glass substrate B5.

[0148] (Conductive material layer forming process)

The obtained glass substrate B5 was immersed in a 1.0% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 minute, washed with water, and dried with an air gun. After that, electroless plating was performed by immersing in an electroless plating bath (pH: 12.4) having the following composition for 30 minutes. After electroless plating, it was washed with water and dried with an air gun.

Composition of electroless bath

300 g of water

Copper (II) sulfate pentahydrate 3.0 g

EDTA— 2Na dihydrate 8.9 g

Polyethylene glycol (average molecular weight 1000) 0.03g

2, 2'—Bibiridinole 0.3 mg

Ethylenediamine 0.12g

Sodium hydroxide 2.5g

Honolem Norede Dehydrated Water ί 夜（36. 0—38. 0%) 1. 6g

[0149] When this surface was observed with an electron microscope (Miniscope TM—1000 manufactured by HITACHI), a conductive pattern 5 in which a line width of 10 m and a gap width of 10 m exist alternately was formed! / ヽ It was confirmed that

[0150] Example 6

(Photocleavable compound binding process)

The surface of the glass substrate (Nippon Sheet Glass) was cleaned by UV ozone treatment for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.), and the substrate was washed with 3-aminopropyltrimethoxysilane 1 It was immersed in a weight% aqueous solution for 10 minutes, washed with water, and dried with an air gun.

Next, the exemplified compound T9 dehydrated E chill methyl ketone (2-butanone) to be 10 mass ^_0/0 solution prepared Te溶力, it was spin-coated on the substrate surface. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 120 ° C. for 40 minutes, and the surface was washed with ethyl methyl ketone. Thereafter, the substrate A6 was dried with an air gun to obtain a substrate A6 having a polymerization initiating layer formed by binding the exemplified compound T1 to a glass substrate (the thickness of the polymerization initiating layer: 2.6 m).

[0151] (Graft polymer production process)

The coating solution for forming a graft polymer precursor layer was spin-coated on one surface of the substrate A6 obtained above. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. Substrate A6 after application of the coating solution for the graft forming layer was dried at 80 ° C. for 5 minutes to form a graft polymer precursor layer.

[0152] (Exposure)

The substrate A6 after the formation of the graft polymer precursor layer was exposed in accordance with a predetermined pattern using an exposure machine (UNIKIURE UVX-02516 S 1LP01, manufactured by Usio Electric Co., Ltd.). After the exposure, the substrate surface was washed with water while gently rubbing with a wiper (Bencot, manufactured by Ozu Sangyo Co., Ltd.) and washed with Aceton for 7 fires.

As described above, a glass substrate B6 having a graft polymer layer formed in a pattern on the surface was formed. The obtained pattern was observed with AFM (Nanobics 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a pattern having a line width of 10 m and a gap width of 10 mm was alternately formed on the surface of the glass substrate B6.

[0153] (Conductive material layer forming process)

The obtained glass substrate B6 was immersed in a 1.0% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 minute, washed with water, and dried with an air gun.

Next, it was immersed in a commercially available electroless plating bath ATS AD Kappaichi (Okuno Pharmaceutical Co., Ltd.) having the following composition for 30 minutes for electroless plating. After electroless plating, it was washed with water and dried with an air gun.

[0154] Composition of electroless bath

258g of water

ATS Ad Kappa IW— A 15mL

ATS Ad Kappa IW— M 24mL

ATS Ad Kappa IW— C 3mL

[0155] When this surface was observed with an electron microscope (Miniscope TM—1000 manufactured by HITACHI), it was confirmed that a conductive pattern 6 in which a line width of 10 m and a gap width of 10 m exist alternately was formed! It was done.

[0156] Example 7

(Photocleavable compound binding process)

Surface cleaning was performed on a glass substrate (Nippon Sheet Glass) by UV ozone treatment for 10 minutes using a UV ozone cleaner (UV42, manufactured by Nippon Laser Electronics Co., Ltd.). A 10 mass% aqueous solution of 3-aminopropyltriethoxysilane (manufactured by Tokyo Kasei) was spin-coated on the glass substrate. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 120 ° C. for 20 minutes, and the substrate was taken out, washed with distilled water, and dried.

[0157] Next, the exemplified compound 15 mass ^_0/0 solution was prepared by dissolving the T10 dehydrated E chill methyl ketone (2-butanone), was spin-coated it to the substrate surface. Spin coater First, it was rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 170 ° C. for 1 hour and the surface was washed with ethyl methyl ketone. Thereafter, it was dried with an air gun to obtain a substrate A7 having a polymerization initiation layer formed by binding Exemplified Compound T10 to a glass substrate (the thickness of the polymerization initiation layer: 3.7 m).

[0158] (Graft polymer production process)

0.5 g of the hydrophilic polymer P2 obtained in Synthesis Example 4 was dissolved in 2 methoxy-l-propanol to obtain a coating solution for a graft forming layer.

A coating solution for forming a graft polymer precursor layer was spin-coated on one surface of the substrate A3 obtained above. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. Substrate A7 after application of the coating solution for forming the graft polymer precursor layer was dried at 80 ° C. for 5 minutes to form a graft polymer precursor layer.

[0159] (Exposure)

The substrate A2 after the formation of the graft polymer precursor layer was exposed in accordance with a predetermined pattern using an exposure machine (UNIKIURE UVX-02516 S 1LP01, manufactured by Usio Electric Co., Ltd.). After the exposure, the substrate surface was washed with water while gently rubbing with a wiper (Bencot, manufactured by Ozu Sangyo Co., Ltd.) and washed with Aceton for 7 fires.

As described above, a glass substrate B7 having a graft polymer formed in a pattern on the surface was formed.

[0160] The obtained pattern was observed with AFM (Nanobix 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a pattern having a line width of 10 m and a gap width of 10 mm was alternately formed on the surface of the glass substrate B7.

[0161] (Conductive material layer formation process)

The obtained glass substrate B7 was immersed in a 1.0% aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 minute, washed with water, and dried with an air gun. Thereafter, electroless plating was performed by immersing in the electroless plating bath (pH: 12.4) described in Example 1 for 30 minutes. After electroless plating, it was washed with water and dried with an air gun.

[0162] This surface was observed with an electron microscope (Miniscope TM—1000 manufactured by HITACHI). It was confirmed that a conductive pattern 7 having a filtration line width of 10 m and a gap width of 10 m alternately formed was formed.

[0163] Comparative Example 1

In Example 1, the same process as in Example 1 was performed, except that the following compound T7 was used instead of the exemplified compound T1, and the exemplified compound P4 (see below) was used instead of the hydrophilic polymer P1. Here, as the following compound T7, a compound described in JP-A-2006-104045 was used.

When an attempt was made to form a conductive material layer (conductive film) with a conductive film thickness of 1 11 m or more, it peeled off during the electroless plating process.

[0164] [Chemical 6]

[0165] <Evaluation of conductivity and film thickness>

For the conductive patterns obtained in the examples and comparative examples, the surface conductivity of the portion where the conductive film was formed was measured by a four-probe method using Lorester FP (LORESTA-FP: manufactured by Mitsubishi Chemical Corporation). The film thickness was measured using Nanopixl 000 (manufactured by Seiko Instruments Inc.). The results are shown in Table 1.

[0166] <Evaluation of adhesion of conductive film>

Examples: Conductive regions (conductive film) (10 (mm) X 200 (mm)) were formed in the same manner as in! To 4, and applied to the cut grid according to JIS 5400 grid pattern tape method. A tape peeling test was conducted to evaluate film adhesion. Table 1 shows the number of boards remaining on the board side among the 100 grids.

[0167] Comparative Example 2 (Photocleavable compound binding process)

Next, a 0.07% by mass solution of the exemplified compound T2 in dehydrated ethylmethylketone (2-butanone) was prepared, and this was spin-coated on the substrate surface. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After spin coating, the glass substrate was heated at 170 ° C. for 1 hour, and the surface was washed with ethyl methyl ketone. Thereafter, it was dried with an air gun to obtain a substrate A9 having a polymerization initiating layer formed by binding Exemplified Compound T2 to a glass substrate (polymerization initiating layer thickness: 20 nm).

[0168] (Graft polymer production process)

0.5 g of the hydrophilic polymer P2 obtained in Synthesis Example 4 above is dissolved in a mixed solvent of sodium hydrogen carbonate aqueous solution 4.62 g, dimethylacetamide (DMAc) O. 05 g, and acetonitrile-1.5 g of graft polymer precursor. A coating solution for the layer forming layer was obtained.

The coating liquid for graft polymer precursor layer formation layer was spin-coated on one surface of the substrate A9 obtained above. The spin coater was first rotated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. Substrate A9 after applying the coating solution for the graft polymer precursor layer forming layer was dried at 80 ° C. for 5 minutes to form a graft polymer precursor layer.

[0169] (Exposure)

The substrate A9 after the formation of the graft polymer precursor layer was exposed in accordance with a predetermined pattern using an exposure machine (UNIKIURE UVX-02516 S 1LP01, manufactured by Usio Electric Co., Ltd.). After the exposure, the substrate surface was washed with water while gently rubbing with a wiper (Bencott, manufactured by Ozu Sangyo Co., Ltd.) and washed with Aceton for 7 fires.

As described above, a glass substrate B9 having a graft polymer layer formed in a pattern on the surface was formed.

[0170] The obtained pattern was observed with AFM (Nanobix 1000, manufactured by Seiko Instruments Inc., using DFM cantilever). As a result, it was confirmed that a pattern in which a line width of 10 m and a gap width of 10 μm exist alternately was formed on the surface of the glass substrate B9.

[0171] (Conductive material layer forming process) <Electroless plating>

Next, it was immersed in a commercially available electroless plating bath ATS AD Kappaichi (Okuno Pharmaceutical Co., Ltd.) with the following composition for 30 minutes to perform the electroless plating process, but it peeled off during the treatment.

[table 1]

[0173] From the above results, it was confirmed that the conductive regions in the conductive patterns 1 to 7 obtained by the method of the present invention have good conductivity and excellent adhesion to the substrate. It was. On the other hand, the conductive films of Comparative Examples 1 and 2 were peeled off during the electroless plating process, and no conductive pattern was obtained.

[0174] The disclosures of Japanese applications 2006-264706, 2007-047719, and 2007-223870 are hereby incorporated by reference in their entirety. All documents, patent applications, and technical standards mentioned in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. And incorporated herein by reference.

Claims

The scope of the claims

[1] glass substrates,

A polymerization initiating layer having a thickness of 0 · 111 m or more and 100 am or less formed by a polymer having a radical polymerization initiation site and a site capable of being chemically bonded directly to the glass substrate, chemically bonded to the glass substrate; as well as,

It has a skeleton derived from a structure selected from (meth) acrylic acid ester and (meth) acrylic acid amide in the molecule, and has an unsaturated site capable of radical polymerization and a site that adsorbs an electroless catalyst. A graft polymer precursor layer containing a polymer,

A laminate characterized by comprising:

[2] The laminate according to [1], wherein the radical-polymerizable unsaturated site is a (meth) atalyloylmethyl group.

[3] The polymer having a radical polymerization initiation site and a site capable of being directly chemically bonded to the glass substrate has a weight average molecular weight in the range of 1000 to 1000000. Laminated body.

[4] Site force capable of direct chemical bonding to the glass substrate Halosilyl group, alkoxysilyl group

The laminate according to claim 1, wherein the laminate is a cyclic ether group or an isocyanate group.

[5] The laminate according to [1], wherein the glass base material contains silicon oxide as a main component.

[6] Surface force of the glass substrate modified with at least one functional group selected from amino group, hydroxyl group, mercapto group, carboxyl group, epoxy group and isocyanate group! / The laminate according to claim 1, wherein:

[7] The surface force of the glass substrate is modified by using a silane coupling agent having an amino group, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, or an isocyanate group. The laminated body as described in.

[8] The thickness of the polymerization initiation layer is from 0.3 · 3 am to 50 μm.

The laminate according to 1.

[9] The graft polymer precursor layer has a thickness of 0.3 to 5 m. The laminate according to claim 1.

[10] Energy is imparted in a pattern on the laminate according to claim 1, and radicals are generated at a radical polymerization initiation site of the polymer in the polymerization initiation layer of the laminate, and the radical is originated. Producing a graft polymer as

A step of adsorbing an electroless catalyst or a precursor thereof to the generated graft polymer, followed by electroless plating to form a conductive film;

A method for forming a conductive pattern, comprising:

11. The conductive pattern forming method according to claim 10, further comprising an electroplating treatment step after the step of forming the conductive film.

[12] A conductive pattern formed by using the conductive pattern forming method according to claim 10 or 11.

[13] A printed wiring board comprising the conductive pattern according to claim 12.

14. A thin layer transistor comprising the conductive pattern according to claim 12.

15. An apparatus comprising the printed wiring board according to claim 13.

16. A device comprising the thin film transistor according to claim 14.