JP2009038131A - Wiring and manufacturing method thereof, and electronic component and electronic equipment using wiring - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wiring having a single conductive particulate layer or a plurality of conductive particulate layers holding original functions of conductive particulates without impairing them and selectively arrayed on an arbitrary base material surface, to provide a manufacturing method thereof, and to provide an electronic component and electronic equipment using the wiring. <P>SOLUTION: Disclosed are a patterned wiring 1 or 3 where one conductive particulate layer having conductive particulates 31 arrayed is bonded and fixed only to a pattern portion 22 of a surface of a base material 11, where a coating 13 of a first film compound having a first functional group at one end of a molecule is formed at the pattern portion 22 of the surface of the base material, and a coating 33 of a second compound having a second functional group at one end of a molecule is formed on a surface of the conductive particulates 31, which are fixed on the base material 11 through a bond formed through coupling reaction between the first and second functional group and a first coupling agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a conductor wiring used for an electronic device or a printed circuit board, a manufacturing method thereof, an electronic component using the wiring, and an electronic apparatus. More specifically, the present invention relates to a wiring having conductive fine particles introduced with a functional group having reactivity on the surface, a manufacturing method thereof, an electronic component and an electronic device using the wiring.

Conventionally, as a conductor wiring used for an electronic device or a printed circuit board and a manufacturing method thereof, a conductive paste selectively applied in a predetermined pattern by a method such as screen printing or photolithography is heat-treated to form a wiring. A method (for example, refer to Patent Documents 1 and 2), a method for selectively removing a conductor layer on a substrate surface by using a photolithography method and an etching method (for example, refer to Patent Document 3), etc. It has been known.

JP 2004-356053 A JP 2004-273205 A JP 2002-124518 A

However, printing and photolithography have not been able to fully cope with the miniaturization and density increase of electronic devices and printed boards.

On the other hand, in order to miniaturize the wiring on an electronic device or a printed board, it is necessary to form a conductive fine particle on the board with a uniform film thickness. However, a conductive fine particle layer composed of conductive fine particles having a uniform thickness at a particle size level, in which only one layer of conductive fine particles is arranged on an arbitrary substrate surface, and a conductive fine particle layer in which a plurality of layers are accumulated, and those A manufacturing method has not yet been developed and provided, and a technical idea of controlling the film thickness of the conductive fine particle film according to the size of the conductive fine particles used and the number of stacked layers has not been proposed so far.

The present invention retains the original function of the conductive fine particles without impairing the function, and comprises a single-layer conductive fine particle layer or a plurality of conductive fine particle layers selectively arranged on the surface of an arbitrary substrate and its wiring An object of the present invention is to provide a manufacturing method and an electronic component and an electronic device using wiring.

The wiring according to the first aspect of the present invention is a patterned wiring in which a conductive fine particle layer in which conductive fine particles are arranged only on a pattern portion on the surface of a base material is bonded and fixed. A film of a first film compound having a first functional group at one end of the molecule and bonded to the surface of the pattern portion at the other end is formed on the pattern portion of the surface of the conductive fine particles. Has a second functional group at one end of the molecule and a film of a second film compound bonded to the surface of the conductive fine particle at the other end. The conductive fine particle has the first functional group. At least one first coupling reactive group that forms a bond by coupling reaction with a group, and at least one second coupling reactive group that forms a bond by coupling reaction with the second functional group; A first coupling agent having: and the first Are fixed on the substrate via a bond formed by the coupling reaction between the fine said second functional group.

In the wiring according to the first invention, it is preferable that the first film compound and the second film compound are the same compound.

In the wiring according to the first invention, it is preferable that one or both of the coatings formed by the first and second film compounds are monomolecular films.

In the wiring according to the first aspect, the bond formed by the coupling reaction may be an N—CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group.

In the wiring according to the second invention, the conductive fine particle layer in which conductive fine particles are arranged only on the pattern portion on the surface of the base material, the first layer to the nth layer from the base material side toward the interface with the air. A pattern-like wiring that is sequentially laminated up to a layer (n is an integer of 2 or more), wherein the pattern portion on the surface of the substrate has a first functional group at one end of a molecule and the other end at the other end A film of the first film compound bonded to the surface of the pattern portion is formed, the surface of the first layer of the conductive fine particles has a second functional group at one end of the molecule, and the conductive at the other end. The surface of the conductive fine particles forming the x-th (x is an integer, 2 ≦ x ≦ n) is formed as a film of the second film compound bonded to the surface of the fine particles. Coated with a film formed of the (x + 1) th film compound having the (x + 1) th functional group, The first layer of particles is coupled to at least one first coupling reactive group that forms a bond by coupling reaction with the first functional group, and forms a bond by coupling reaction with the second functional group. A first coupling agent having at least one second coupling reactive group, and on the substrate via a bond formed by a coupling reaction between the first and second functional groups. The (x-1) th layer and the xth layer of the conductive fine particle layer are fixed, and at least one xth coupling reactive group that forms a bond through a coupling reaction with the xth functional group. An x-th coupling agent having at least one (x + 1) -th coupling reactive group that forms a bond by reacting with the (x + 1) -th functional group, the x-th functional group, and Xth coupling anti Fixed to each other through a bond formed by a coupling reaction with a group and a bond formed by a coupling reaction between the (x + 1) th functional group and the (x + 1) coupling reaction group .

In the wiring according to the second invention, it is preferable that the first to (n + 1) th film compounds and the first to nth coupling agents are the same compound.

In the wiring according to the second invention, it is preferable that all the films formed by the first to (n + 1) th film compounds are monomolecular films.

In the wiring according to the second invention, the bond formed by the coupling reaction may be an N—CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group.

A wiring manufacturing method according to a third invention is a method of manufacturing a patterned wiring in which a conductive fine particle layer in which conductive fine particles are arranged only on a pattern portion on the surface of a substrate is bonded and fixed. A solution containing a first film compound having a first functional group and a first binding group at both ends is brought into contact with the surface of the base material, and between the first binding group and the surface of the base material Forming a bond and coating the surface of the substrate with a coating formed by the first film compound, and irradiating the surface of the coated substrate with energy rays through a mask covering the pattern portion And performing a pattern forming process for leaving a film formed by the first film compound only on the pattern portion, and a second film having a second functional group and a second binding group at both ends of the molecule, respectively. The solution containing the compound is converted into the conductive fine particles. Forming a film formed by the second film compound on the surface of the conductive fine particles by contacting the surface of the conductive fine particles to form a bond between the second bonding group and the surface of the conductive fine particles. A coupling reaction with the first functional group to form a bond and one or more first coupling reactive groups to form a bond with the second functional group to form a bond. Conductive fine particles in which a first coupling agent having one or two or more second coupling reactive groups, a substrate subjected to the pattern formation treatment, and a film of the second film compound are formed. The first functional group and the first coupling reactive group, and the second functional group and the second coupling reactive group by a coupling reaction. Previously through the formed bond The conductive fine particle layer of one layer of conductive fine particles are bound and fixed to the surface of the substrate and then, a step D of removing the conductive fine particles were not fixed on the surface of the substrate.

In the wiring manufacturing method according to the third invention, the pattern forming process in the step B may be performed by removing the film of the first film compound other than the pattern portion by using a laser ablation method. Good.

In the wiring manufacturing method according to the third invention, the pattern forming process in the step B is performed by converting the first functional group other than the pattern part into another functional group by irradiation with the energy beam. May be.

In the wiring manufacturing method according to the third invention, in the step D, first, the first coupling agent is brought into contact with the surface of the substrate on which the pattern forming treatment has been performed, and the first functional group and the A film of the first coupling agent is selectively formed only on the surface of the pattern portion through a bond formed by a coupling reaction with a first coupling reactive group, and then the first coupling agent is formed. A base material on which a coating film of a coupling agent is formed and a conductive fine particle on which a coating film of the second film compound is formed are brought into contact with each other, and a cup of the second functional group and the second coupling reactive group is obtained. The conductive fine particles may be selectively bonded and fixed only to the surface of the pattern portion through a bond formed by a ring reaction.

In the wiring manufacturing method according to the third invention, in the step D, first, the first coupling agent is brought into contact with the surface of the conductive fine particles on which the coating of the second film compound is formed, and the first A coating of the first coupling agent is further formed on the surface via a bond formed by a coupling reaction between the functional group of 2 and the second coupling reactive group, and then the first cup The conductive fine particles on which the coating film of the ring agent was formed and the substrate subjected to the pattern formation treatment were brought into contact with each other, and formed by a coupling reaction between the first functional group and the first coupling reactive group. The conductive fine particles may be selectively bonded and fixed only to the surface of the pattern portion through bonding.

In the wiring manufacturing method according to the third invention, it is preferable that the first film compound and the second film compound are the same compound.

In the method for manufacturing a wiring according to the third invention, in the step A and the step C, the unreacted first and second film compounds are washed and removed on the surfaces of the base material and the conductive fine particles. The films formed by the first and second film compounds are preferably monomolecular films.

In the method for manufacturing a wiring according to a third aspect of the invention, the conductive fine particle layer is formed on the substrate from the first layer to the nth layer (n is 2 or more) from the substrate side toward the interface with the air. In which a solution containing a third film compound having a third functional group and a third bonding group at each end of the molecule is brought into contact with the surface of the conductive fine particles. And forming a bond between the third bonding group and the surface of the conductive fine particles to form a film of the third film compound on the surface of the conductive fine particles, and then the third film. On the surface of the conductive fine particle on which the coating film of the compound is formed, the second coupling reactive group and one or two or more third functional groups that form a bond through a coupling reaction with the third functional group Contacting a second coupling agent having a coupling reactive group, The second cup is formed on the surface of the conductive fine particles on which the coating film of the third film compound is formed through a bond formed by a coupling reaction between the functional group 3 and the third coupling reactive group. A step E of further forming a coating film of a ring agent; a conductive fine particle on which a film of the second film compound located on a surface layer of the conductive fine particle layer is formed; and a film of the second coupling agent is formed. The coating film of the second coupling agent is formed through the bond formed by the coupling reaction between the second functional group and the second coupling reactive group. The conductive fine particles are bonded and fixed onto the conductive fine particles on which the coating of the second film compound is formed, and then the conductive fine particles on which the coating of the second coupling agent that has not been bonded and fixed is formed To remove And when n ≧ 3, the film of the second film compound is formed on the surface of the conductive fine particles having the film of the second coupling agent located on the surface layer of the conductive fine particle layer. Conductive film in which the film of the second film compound is formed through a bond formed by a coupling reaction between the second functional group and the second coupling reactive group. The fine particles are bonded and fixed onto the conductive fine particles on which the coating film of the second coupling agent is formed, and then the conductive fine particles on which the coating film of the second film compound that has not been bonded and fixed is formed is removed. The method further includes a step G. If n ≧ 4, the method may further include a step H in which the steps F and G are alternately repeated until the n conductive fine particle layers are formed.

In the wiring manufacturing method according to the third invention, it is preferable that the first to third film compounds are the same compound.

In the wiring manufacturing method according to the third invention, in the step E, the unreacted third film compound is washed away, and the film formed by the third film compound on the surface of the conductive fine particles is A monomolecular film is preferable.

In the method for manufacturing a wiring according to a third aspect of the invention, the conductive fine particle layer is formed on the substrate from the first layer to the nth layer (n is 2 or more) from the substrate side toward the interface with the air. And a solution containing a third film compound having the first functional group and the third bonding group at both ends of the molecule on the surface of the conductive fine particles. Contacting E, forming a bond between the third bonding group and the surface of the conductive fine particles, and forming a film formed by the third film compound on the surface of the conductive fine particles; Contacting the conductive fine particles formed with the first coupling agent film located on the surface layer of the conductive fine particle layer with the conductive fine particles formed with the film of the third film compound, the first fine particles are brought into contact with each other. Coupling reaction between the functional group and the first coupling reactive group The conductive fine particles on which the film of the third film compound is formed are bonded and fixed on the conductive fine particles on which the film of the first coupling agent is formed through the bond formed by And a step F of removing the conductive fine particles on which the film of the third film compound that has not been bonded and fixed is formed, and when n ≧ 3, the third fine particles located on the surface layer of the conductive fine particle layer The conductive fine particles on which the film of the film compound is formed and the conductive fine particles on which the film of the first coupling agent is formed are brought into contact with each other, and the first functional group and the first coupling reactive group The conductive fine particles on which the coating film of the first coupling agent is formed are bonded and fixed on the conductive fine particles on which the coating film of the third film compound is formed through a bond formed by a coupling reaction, Then the bond was not fixed The method further includes a step G of removing the conductive fine particles on which the first coupling agent film is formed. When n ≧ 4, the steps F and G are performed until the n conductive fine particle layers are formed. The process H which repeats alternately may be further included.

In the wiring manufacturing method according to the third invention, the first and second film compounds, or the first to third film compounds are all alkoxysilane compounds, and the first and second film compounds, Alternatively, the solution containing the first to third film compounds may further contain, as a condensation catalyst, a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate, and titanate. One or more compounds selected from the group consisting of ester chelates may be included.
In this case, the cocatalyst may further contain one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds. .

In the wiring manufacturing method according to the third invention, the first and second film compounds, or the first to third film compounds are all alkoxysilane compounds, and the first and second film compounds, Alternatively, the solution containing the first to third membrane compounds is further selected from the group consisting of a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound as a condensation catalyst. Or it may further contain two or more compounds.

In the method for manufacturing a wiring according to the third invention, the bond formed by the coupling reaction is an N—CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group. Also good.

An electronic component according to a fourth aspect uses the wiring according to the first and second aspects.

An electronic apparatus according to a fifth aspect uses the wiring according to the first and second aspects.

In the wiring according to any one of claims 1 to 8 and the wiring manufacturing method according to claims 9 to 25, an arbitrary film on an arbitrary pattern on an arbitrary substrate without impairing the original function of the conductive fine particles. A pattern-like wiring that can be formed with a large thickness and has a uniform film thickness and little variation in quality can be manufactured at low cost.
In addition, since the conductive fine particle layers arranged on the surface of the base material are bonded and fixed to the surface of the base material, the conductive fine particle layer has high peel resistance and wiring one layer at a time through the bond formed by the coupling reaction. Since the lamination is fixed, the film thickness of the patterned wiring can be easily controlled at the level of the size of the conductive fine particles.
Furthermore, since a binder is not used for laminating and fixing the conductive fine particle layer, a wiring having a high conductor density and high electrical conductivity can be formed.

In the wiring according to claim 2, since the first film compound and the second film compound are the same compound, the manufacturing cost can be reduced.

In the wiring according to claim 3, since one or both of the films formed by the first and second film compounds are monomolecular films, the original physical properties of either or both of the base material and the conductive fine particles There is no loss of functionality.

In the wiring according to claim 4, the bond formed by the coupling reaction is an N—CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group. A strong bond can be formed.

6. The wiring according to claim 5, wherein the conductive fine particle layer is formed by sequentially laminating the conductive fine particle layer from the substrate side toward the interface side with the air, the number of the conductive fine particle layers laminated, and each conductive fine particle. Since the material, particle size, and the like of the conductive fine particles constituting the layer can be arbitrarily determined, the film thickness, electrical conductivity, etc. of the conductive fine particle layer can be easily controlled. In addition, an optimal film compound and coupling agent can be selected according to the material of each conductive fine particle layer.

In the wiring according to claim 6, since each of the first to (n + 1) th film compounds and the first to nth coupling agents is the same compound, the manufacturing cost can be further reduced.
In the wiring according to claim 7, since all the films formed by the first to (n + 1) th film compounds are monomolecular films, the original physical properties and functions of the base material and the conductive fine particles are not impaired. .

In the wiring according to claim 8, since the bond formed by the coupling reaction is an N—CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group, A strong bond can be formed.

In the wiring manufacturing method according to claim 10, the pattern forming process in the step B is performed by removing the coating of the first film compound other than the pattern portion by using the laser ablation method. Can be formed with high accuracy.

In the wiring manufacturing method according to claim 11, the pattern forming process in the step B is performed by converting the first functional group other than the pattern part into another functional group by irradiation with energy rays. Accurate patterns can be formed with high accuracy.

In the wiring manufacturing method according to claim 12, in step D, first, the first coupling agent is brought into contact with the surface of the substrate on which the pattern formation process has been performed, so that the first functional group and the first cup are brought into contact with each other. A first coupling agent film is selectively formed only on the surface of the pattern portion via a bond formed by a coupling reaction with the ring reactive group, and then a first coupling agent film is formed. Through the bond formed by the coupling reaction between the second functional group and the second coupling reactive group, by contacting the formed substrate and the conductive fine particles on which the coating of the second film compound is formed. Since the conductive fine particles are selectively bonded and fixed only to the surface of the pattern portion, the second functional group and the conductive fine particles covered with the coating formed by the second film compound are not subjected to pretreatment. Second coupling reactive group The coupling reaction, the conductive fine particles covered with a film forming the second film compound can be bound and fixed to the surface.

In the wiring manufacturing method according to claim 13, in step D, first, the first coupling agent is brought into contact with the surface of the conductive fine particles on which the film of the second film compound is formed, and the second functional A first coupling agent film is further formed on the surface of the first coupling agent film via a bond formed by a coupling reaction between the group and the second coupling reactive group, and then a first coupling agent film is formed. Only the surface of the pattern part is brought into contact with the formed conductive fine particles and the base material subjected to the pattern forming treatment through a bond formed by a coupling reaction between the first functional group and the first coupling reactive group. Since the conductive fine particles are selectively bonded and fixed to the first functional group, the first functional group and the first coupling reaction can be performed without pretreatment of the base material covered with the coating film formed by the first film compound. For coupling reactions with groups Ri can be the first film compound conductive particles covered with a film forming the second film compound-covered surface of the substrate with a film formed of bonded stationary.

In the wiring manufacturing method according to the fourteenth aspect, since the first film compound and the second film compound are the same compound, the manufacturing cost can be reduced.

In the wiring manufacturing method according to claim 15, since the coating formed by the first and second film compounds is a monomolecular film, the original physical properties and functions of the base material and the conductive fine particles may be impaired. Absent.

In the wiring manufacturing method according to the sixteenth aspect, since a wiring with an arbitrary film thickness can be manufactured using three kinds of film compounds and two kinds of coupling agents, the manufacturing cost can be reduced.

In the wiring manufacturing method according to the seventeenth aspect, since the first to third film compounds are the same compound, the manufacturing cost can be further reduced.
In the wiring manufacturing method according to claim 18, since the coating film formed by the third film compound is a monomolecular film, the original physical properties and functions of the conductive fine particles are not impaired.

In the wiring manufacturing method according to the nineteenth aspect, since a wiring with an arbitrary film thickness can be manufactured using three types of film compounds and one type of coupling agent, the manufacturing cost can be reduced.

In the method for manufacturing a wiring according to claim 20 and 22, a solution containing a film compound is further used as a condensation catalyst as a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, Since one or two or more compounds selected from the group consisting of titanate esters and titanate ester chelates are included, the time required for forming the film of the film compound is shortened, and the wiring is manufactured more efficiently. be able to.

25. The method of manufacturing a wiring according to claim 21, 23 and 24, wherein the solution containing the film compound is selected from the group consisting of a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound. Since it further includes one or two or more compounds, the time required for forming the film of the film compound can be shortened, and the wiring can be manufactured more efficiently. In particular, when both of these compounds and the above condensation catalyst are included, the preparation time can be further shortened.

In the wiring manufacturing method according to claim 25, the bond formed by the coupling reaction is an N—CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group. A strong bond can be formed by heating.

In the electronic component of the wiring according to claim 26 and the electronic device according to claim 27, since the wiring according to claims 1 to 8 having high electrical conductivity and high peel resistance is used, internal loss and There is little heat generation with it, and it is excellent in reliability and durability.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention.
Here, FIG. 1A is an explanatory view schematically showing a cross-sectional structure of the patterned single-layer wiring according to the first embodiment of the present invention, and FIG. 1B is a second view of the present invention. FIG. 2A schematically illustrates a cross-sectional structure of the patterned single-layer wiring according to the third embodiment of the present invention. FIG. 2A schematically illustrates the cross-sectional structure of the patterned multilayer wiring according to the embodiment. FIG. 2B is an explanatory diagram schematically showing the cross-sectional structure of the patterned laminated wiring according to the fourth embodiment of the present invention, and FIG. 3 is the first diagram of the present invention. In the manufacturing method of the patterned wiring which concerns on 4th Embodiment, it is the conceptual diagram expanded to the molecular level in order to demonstrate the process of forming the film of the 1st film compound on the surface of a glass substrate, 3 (a) is a cross-sectional structure of the glass substrate before the reaction, and FIG. 3 (b) is a monomolecular film of a film compound having an epoxy group. Each of the cross-sectional structures of the formed glass substrate is shown, and FIG. 4 (a) is a conceptual diagram enlarged to the molecular level for explaining the process of performing the pattern forming process in the manufacturing method of the same wiring. FIG. 5 is a conceptual diagram enlarged to a molecular level to explain a process of performing a pattern forming process according to a modified example, and FIG. 5 is a diagram of silver fine particles in the wiring manufacturing method according to the first to fourth embodiments of the present invention. FIGS. 5A and 5B are conceptual diagrams enlarged to a molecular level to explain a process of forming a film of the second film compound on the surface, FIG. 5A is a cross-sectional structure of silver fine particles before reaction, and FIG. Each represents a cross-sectional structure of silver fine particles on which a monomolecular film of a film compound having a group is formed.

Next, the single-layer wiring 1 according to the first embodiment of the present invention will be described.
As shown in FIG. 1 (a), the single-layer wiring 1 has a silver fine particle layer (conducting conductive material) in which silver fine particles 31 (an example of conductive fine particles) are arranged only in a pattern portion on the surface of a glass substrate 11 (an example of a base material). An example of the conductive fine particle layer is a pattern-like wiring in which one layer is bonded and fixed.
A monomolecular film 13 of a first film compound having an epoxy group (an example of a first functional group) at one end of the molecule on the pattern portion on the surface of the glass substrate 11 and bonded to the surface of the pattern portion at the other end. (An example of a coating film) is formed, and further, an amino group and an imino group (an example of first and second coupling reactive groups) that form a bond by coupling reaction with an epoxy group are formed on the surface of the film. A monomolecular film 15 of 2-methylimidazole fixed via a bond formed by a coupling reaction between an amino group and an epoxy group of 2-methylimidazole (an example of a first coupling agent) having one by one ( An example of a film is formed.
A monomolecular film 33 (an example of a coating film) of a second film compound having an epoxy group (an example of a second functional group) at one end of the molecule on the surface of the silver fine particle 31 and bonded to the surface of the silver fine particle 31. Is formed.
The glass substrate 11 and the silver fine particles 31 are bonded and fixed to each other through a bond formed by a coupling reaction between an epoxy group and an amino group or imino group of 2-methylimidazole.

The manufacturing method of the single-layer wiring 1 has an epoxy group as shown in FIGS. 3A, 3B, 4A, 5A, 5B, and 1A. A solution containing an alkoxysilane compound (an example of a first film compound) is brought into contact with the surface of the glass substrate 11, and an alkoxysilyl group (an example of a first bonding group) and a hydroxyl group 12 on the surface of the glass substrate 11 are contacted. A monomolecular film of the first film compound is formed through a step A (see FIG. 3) for forming a bond and forming a monomolecular film 13 of the first film compound on the surface of the glass substrate 11 and a mask 21 covering the pattern portion. Step B (see FIG. 4) in which pattern formation processing is performed in which light irradiation (irradiation of energy rays) is performed on the surface 13 and an epoxy group is left only in the pattern portion 22, and an alkoxysilane compound having an epoxy group (One of the second membrane compounds ) Is brought into contact with the surface of the silver fine particles 31, a bond is formed between the alkoxysilyl group (an example of the second bonding group) and the hydroxyl groups 32 on the surface of the silver fine particles 31, and the second Step C (see FIG. 5) for forming the monomolecular film 33 of the film compound, and first, 2-methylimidazole is brought into contact with the glass substrate 11 subjected to the pattern forming treatment to couple the epoxy group and the amino group. A glass substrate on which the monomolecular film 15 of 2-methylimidazole is selectively formed only on the surface of the pattern portion 22 through the bond formed by the reaction, and then the monomolecular film 15 of 2-methylimidazole is formed. 11 and the silver fine particles 31 on which the monomolecular film 33 of the second film compound is formed are brought into contact with each other, and a pattern portion is formed through a bond formed by a coupling reaction between an epoxy group and an imino group. Selectively fine silver particles 31 only on the surface of the 22 fixed, then, a step D of removing the silver particles 31 which have not been fixed.

Hereinafter, the processes A to D will be described in more detail.
In step A, a film compound having an epoxy group is brought into contact with the glass substrate 11 to form a monomolecular film 13 of the first film compound (see FIG. 3).
The size of the glass substrate 11 is not particularly limited.

As the film compound having an epoxy group, any compound that can be adsorbed or bonded to the surface of the glass substrate 11 and can form a monomolecular film by self-assembly can be used. An alkoxysilane compound having a functional group containing an epoxy group (oxirane ring) at the terminal and an alkoxysilyl group at the other terminal and represented by the following general formula (Formula 1) is preferable.

In the above formula, E represents a functional group having an epoxy group, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms.
Specific examples of the film compound having an epoxy group that can be used include alkoxysilane compounds shown in the following (1) to (12).

(1) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) _{3
(2) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OCH 3) 3
(3) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) _{3
(4) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OCH 3) 3
_{(5) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
(6) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₆ Si (OCH ₃ ) _{3
(7) (CH 2 OCH)} CH 2 O (CH 2) 3 Si (OC 2 H 5) 3
_{(8) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OC 2 H 5) 3
(9) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) ₃
(10) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₂ Si (OC ₂ H ₅ ) _{3
(11) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
_{(12) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OC 2 H 5) 3

Here, the (CH ₂ OCH) CH ₂ — group represents a functional group (glycidyl group) represented by Chemical Formula ₂ , and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by Chemical Formula 3. Represents a functional group (3,4-epoxycyclohexyl group).

Formation of the monomolecular film 13 of the first film compound on the surface of the glass substrate 11 includes condensation of an alkoxysilane compound containing an epoxy group and an alkoxysilyl group, and an alkoxysilyl group and the hydroxyl group 12 on the surface of the glass substrate 11. The reaction is performed by applying a reaction liquid obtained by mixing a condensation catalyst for promoting the reaction and a non-aqueous organic solvent to the surface of the glass substrate 11 and reacting in air at room temperature. The coating can be performed by any method such as a doctor blade method, a dip coating method, a spin coating method, a spray method, or a screen printing method.

As the condensation catalyst, metal salts such as carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates can be used.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, and more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, and iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctyl thioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
Specific examples of titanate chelates include bis (acetylacetonyl) dipropyl titanate.

The alkoxysilyl group and the hydroxyl group 12 on the surface of the glass substrate 11 undergo a condensation reaction to produce a monomolecular film 13 of a first film compound having an epoxy group having a structure represented by the following chemical formula 4. The three single bonds extending from the oxygen atoms are bonded to the surface of the glass substrate 11 or silicon (Si) atoms of the adjacent silane compound, and at least one of them is bonded to the silicon atoms on the surface of the glass substrate 11. is doing.

Since the alkoxysilyl group decomposes in the presence of moisture, the reaction is preferably performed in air with a relative humidity of 45% or less. The condensation reaction is hindered by oils and fats and moisture adhering to the surface of the glass substrate 11, so it is preferable to remove these impurities in advance by thoroughly washing and drying the glass substrate 11.
When any of the above metal salts is used as the condensation catalyst, the time required for completion of the condensation reaction is about 2 hours.

When one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are used as the condensation catalyst instead of the above metal salts The reaction time can be shortened to about 1/2 to 2/3.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (can be used in a mass ratio of 1: 9 to 9: 1, preferably around 1: 1), the reaction time is further shortened. it can.

For example, when the epoxidized silver fine particles 21 are produced by using H3 of Japan Epoxy Resin Co., which is a ketimine compound, instead of dibutyltin bisacetylacetate, which is a carboxylic acid metal salt chelate, as a condensation catalyst, under the same conditions. The reaction time can be shortened to about 1 hour without deteriorating the quality of the epoxidized silver fine particles 21.

In addition, as a condensation catalyst, a mixture of H3 and dibutyltin bisacetylacetonate (mixing ratio is 1: 1) from Japan Epoxy Resin Co., Ltd. Once formed, the reaction time can be reduced to about 20 minutes.

The ketimine compound that can be used here is not particularly limited, and examples thereof include 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza- 3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-penta Decadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza -4,19-trieicosadiene and the like.

Moreover, although it does not specifically limit as an organic acid which can be used, For example, a formic acid, an acetic acid, propionic acid, a butyric acid, malonic acid etc. are mentioned.

For the production of the reaction solution, an organic chlorine solvent, a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, and a mixed solvent thereof can be used. In order to prevent hydrolysis of the alkoxysilane compound, it is preferable to remove water from the desiccant or the solvent used by distillation. Moreover, it is preferable that the boiling point of a solvent is 50-250 degreeC.

Specific usable solvents include non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, and alkyl-modified silicone. , Polyether silicone, dimethylformamide and the like.
Furthermore, alcohol solvents such as methanol, ethanol and propanol, or a mixture thereof can also be used.

Fluorocarbon solvents that can be used include fluorocarbon solvents, Fluorinert (manufactured by 3M, USA), Afludo (manufactured by Asahi Glass Co., Ltd.), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Further, an organic chlorine solvent such as dichloromethane or chloroform may be added.

The preferable density | concentration of the alkoxysilane compound in a reaction liquid is 0.5-3 mass%.

After the reaction, the surface is covered with the monomolecular film 13 of the first film compound having an epoxy group by washing with a solvent and removing excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted substances. A glass substrate 14 is obtained. A schematic view of the cross-sectional structure of the epoxidized glass substrate 14 manufactured in this way is shown in FIG.

As the cleaning solvent, any solvent that can dissolve the alkoxysilane compound can be used, but dichloromethane, chloroform, N-methylpyrrolidone, etc., which are inexpensive, have high solubility, and can be easily removed by air drying are preferable. .

After the reaction, when the surface of the glass substrate 11 is left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the generated silanol group becomes an alkoxysilyl group. Causes a condensation reaction. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the epoxidized glass substrate 14. This polymer film is not necessarily all fixed to the surface of the glass substrate 11 by a covalent bond, but contains an epoxy group, and therefore has the same reactivity as the monomolecular film 13 of the first film compound. Have. Therefore, even if cleaning is not performed, there is no particular hindrance to the manufacturing process after Step B.

In the present embodiment, an alkoxysilane compound having an epoxy group is used. However, the linear alkylene group has an amino group at one end and an alkoxysilyl group at the other end. An alkoxysilane compound represented by the formula (Formula 5) may be used. In addition, as a coupling agent which reacts with an imino group or an amino group, what has a glycidyl group at both ends can be used.

In the above formula, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms.
Specific examples of the film compound having an amino group that can be used include alkoxysilane compounds shown in the following (21) to (28).

(21) H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃
(22) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(23) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(24) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(25) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(26) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(27) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(28) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

However, in this case, among the condensation catalysts that can be used in the reaction solution, a compound containing a tin (Sn) salt reacts with an amino group to form a precipitate, and therefore, with respect to an alkoxysilane compound having an amino group. Cannot be used as a condensation catalyst.
Therefore, when using an alkoxysilane compound having an amino group, excluding carboxylic acid tin salt, carboxylic acid ester tin salt, carboxylic acid tin salt polymer, carboxylic acid tin salt chelate, and an alkoxysilane compound having an epoxy group Similar compounds can be used alone or in combination of two or more as a condensation catalyst.
The types of cocatalysts that can be used and combinations thereof, the types of solvents, the concentration of alkoxysilane compounds, condensation catalysts, and cocatalysts, the reaction conditions, and the reaction time are the same as in the case of alkoxysilane compounds having an epoxy group. Therefore, explanation is omitted.

In the present embodiment, a glass substrate is used as a substrate, but an alkoxysilane compound is also used as a film compound for a substrate made of a material other than glass having an active hydrogen group such as a hydroxyl group or an amino group on its surface. Can be used. Specific examples of such a substrate include transparent electrodes such as ceramics, enamel and ITO (indium tin oxide), metal plates such as aluminum plates, copper plates, aluminum plates, and silicon wafers.
When a synthetic resin is used as the base material, an alkoxysilane compound can be used as the film compound by performing a treatment such as grafting a compound having an active hydrogen group by plasma treatment or the like.

In the present embodiment, a silane compound that undergoes a condensation reaction with active hydrogen groups on the surface of the substrate is used as the first film compound. For example, in the case of a substrate having a gold plating layer, a gold atom is used as the film compound. A thiol derivative or a triazine thiol derivative that forms a strong bond with can be used.
(End of process A)

In step B, the surface of the glass substrate 11 on which the monomolecular film 13 of the first film compound is formed is exposed through the mask 21 covering the pattern portion 22, and only the pattern portion 22 is selectively formed by laser ablation. A pattern forming process is performed leaving the monomolecular film 13 of the film compound 1 (see FIG. 4).
As a mask used for exposure, a mask made of any material that does not transmit light and that is not damaged by irradiation light at least during exposure, such as a reticle material used in photolithography in the manufacture of semiconductor elements, etc. Can do. Further, the exposure may be the same magnification exposure, and the reduction projection exposure may be used when a fine pattern is formed.

As the light source, laser light such as excimer laser such as XeF (353 nm), XeCl (308 nm), KrF (248 nm), ArF (193 nm) is preferably used. As shown in FIG. 4A, irradiation with laser light raises the temperature of the irradiated portion, and the alkoxysilane compound covering the exposed portion is selectively removed (23 in FIG. 4). . As a result, the monomolecular film 13 of the first film compound remains only in the pattern portion 22 (see FIG. 4A).
In order to suppress heat input to portions other than the irradiated portion, it is preferable to remove the epoxidized film compound by a pulse laser ablation method using a pulse laser.
The intensity of the laser light is preferably 0.1 to 0.3 J · cm ⁻² . When the intensity of the laser beam is less than 0.1 J · cm ⁻² , the film compound having an epoxy group cannot be sufficiently removed, and when it exceeds 0.3 J · cm ⁻² , epoxidation is performed. Since the glass member of the glass substrate 14 is removed, neither is preferable.
Moreover, when the intensity | strength of a laser beam is in the said range, as a pulse width, 5-50 ns is preferable.

In the above embodiment, the first film compound is removed by the pulse laser ablation method, but other energy irradiation such as electron beam and X-ray may be used. Further, instead of exposing through the mask, the pattern of the first film compound other than the pattern can be removed by selectively drawing a pattern directly on the monomolecular film 13 of the first film compound with an electron beam or the like. Good.

FIG. 4B shows a pattern forming process according to the modification. In this pattern formation process, after applying a photopolymerization initiator to the surface of the monomolecular film 13 of the first film compound, the surface of the monomolecular film 13 of the first film compound is passed through the mask 21 covering the pattern portion 24. Then, the exposed epoxy group is subjected to ring-opening polymerization to leave the monomolecular film 13 of the first film compound only in the pattern portion 24.
Examples of the photopolymerization initiator that can be used include cationic photopolymerization initiators such as diaryliodonium salts. Examples of the light source include a high-pressure mercury lamp and a xenon lamp.
(End of process B)

In step C, an alkoxysilane compound (second film compound having an epoxy group) similar to that used in step A is brought into contact with silver fine particles 31, and a single molecule of the second film compound having an epoxy group on the surface thereof. A film 33 is formed.

Although there is no restriction | limiting in particular in the particle size of the silver fine particle 31 which can be used, It is preferable to exist in the range of 10 nm-0.1 mm. When the particle size of the silver fine particles 31 is less than 10 nm, the influence of the molecular size of the film compound cannot be ignored. When the particle size exceeds 0.1 mm, the ratio of the mass to the surface area of the silver fine particles 31 is large. Therefore, the mass cannot be supported by the crosslinking reaction.

The formation of the monomolecular film 33 of the second film compound includes the formation of an alkoxysilane compound containing an epoxy group, a condensation catalyst for promoting the condensation reaction between the alkoxysilyl group and the hydroxyl group 32 on the surface of the silver fine particles 31, and a non-aqueous system. The silver fine particles 31 are dispersed in a reaction solution mixed with the organic solvent and reacted in air at room temperature.

Types of alkoxysilane compounds having an epoxy group that can be used in Step C, types of condensation catalyst, types of promoters and combinations thereof, types of solvents, concentrations of alkoxysilane compounds, condensation catalysts, and promoters, reaction conditions, and reactions Since the time is the same as in step A, the description is omitted.

Monomolecular film 33 of the second film compound having an epoxy group having a structure as shown in the above chemical formula 4 by causing a condensation reaction (dealcoholization reaction) between the alkoxysilyl group and the hydroxyl group 32 on the surface of the silver fine particles 31. Is generated. The three single bonds extending from the oxygen atom are bonded to the surface of the silver fine particle 31 or the silicon (Si) atom of the adjacent silane compound, at least one of which is bonded to the silicon atom on the surface of the silver fine particle 31. is doing.
Unlike the case of using a halosilane compound, the surface of the silver fine particles 31 is not corroded by the hydrogen halide generated during the condensation reaction.

After the reaction, it is washed with a solvent, and when the excess alkoxysilane compound and the condensation catalyst remaining on the surface as unreacted substances are removed, as shown in FIG. 5B, a single molecule of the second film compound having an epoxy group Silver fine particles 31 on which the film 33 is formed, that is, epoxidized silver fine particles 34 are obtained.

As the washing solvent, the same washing solvent as in step A can be used.
After the reaction, if the surface of the silver fine particles 31 is left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the generated silanol group becomes an alkoxysilyl group. Causes a condensation reaction. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the epoxidized silver fine particles 34. Although this polymer film is not fixed to the surface of the silver fine particles 31 by a covalent bond, it contains an epoxy group and therefore has the same reactivity as the monomolecular film 33 of the second film compound. Therefore, even if cleaning is not performed, the manufacturing process after the process D is not particularly hindered.

In this embodiment, an alkoxysilane compound having an epoxy group is used. However, as in Step A, an alkoxy group having an amino group at one end of a linear alkylene group and an alkoxysilyl group at the other end is used. Silane compounds may be used.
In the present embodiment, the same alkoxysilane compound as in step A is used, but a different alkoxysilane compound may be used. However, it must have a functional group that reacts with the coupling reactive group of the coupling agent used in Step D to form a bond.

In the present embodiment, silver fine particles are used as the conductive fine particles, but other conductive fine particles can also be used. Other conductive fine particles include copper, nickel, silver-plated noble metal, copper, nickel metal fine particles, and conductive metal oxide fine particles ITO and SnO ₂ .

Even when conductive fine particles other than silver fine particles have an active hydrogen group such as a hydroxyl group or an amino group on their surfaces, an alkoxysilane compound can be used as the second film compound, as in the case of silver. it can.
Further, when the fine particles are gold (Au) having no active hydrogen group on the surface, metal fine particles having Au plated on the surface, or the like, the second bonding group has an —SH group or a triazine thiol group. It is a compound (ω-aminoalkanethiol) represented by a membrane compound (for example, the general formula H ₂ N (CH ₂ ) _n —SH (n is an integer), and specific examples include 3-aminopropanethiol (the above general formula In this case, it is possible to produce gold fine particles in which a monomolecular film of a film compound containing an amino group bonded via a sulfur atom is formed. Of course, a thiol or triazine derivative having an epoxy group can be used instead of an amino group.

In addition, when using silver nanoparticles having a particle size of several nanometers to several tens of nanometers, by increasing the ratio of the surface area to the volume, for example, sintering proceeds by heating at a low temperature of about 230 ° C., It is possible to form a denser and more conductive wire. When such silver nanoparticles are used as conductive fine particles, it is preferable to use a film compound that can be detached from the surface of the silver nanoparticles at a sintering temperature or lower.

In the present embodiment, as the first and second film compounds, both film compounds having an epoxy group are used, but both may be the same compound or different compounds. Furthermore, the first and second film compounds may have different functional groups (for example, one is an epoxy group and the other is an isocyanate group).
(End of process C)

In step D, first, 2-methylimidazole is brought into contact with the glass substrate 11 on which the monomolecular film 13 of the first film compound is formed, that is, the surface of the epoxidized glass substrate 14, and an epoxy group, an amino group, and The silver fine particles 31 are formed by forming the monomolecular film 15 of 2-methylimidazole on the surface through the bond formed by the coupling reaction of, and then forming the monomolecular film 33 of the second film compound on the surface. That is, the epoxidized silver fine particles 34 are brought into contact with each other, and the silver fine particles 31 are bonded and fixed to the surface of the glass substrate 11 through the bond formed by the coupling reaction between the epoxy group and the imino group, and then not fixed. The silver fine particles 31 are removed.

2-Methylimidazole has an amino group and an imino group that react with an epoxy group at the 1-position and 3-position, respectively, and forms a bond by a crosslinking reaction as shown in Chemical Formula 6 below.

The monomolecular film 15 of 2-methylimidazole is formed by applying a reaction solution obtained by mixing 2-methylimidazole and a solvent onto the monomolecular film 13 of the first film compound formed on the surface of the glass substrate 11. The reaction is performed by heating. The coating can be performed by any method such as a doctor blade method, a dip coating method, a spin coating method, a spray method, or a screen printing method.
For the production of the reaction solution, any solvent in which 2-methylimidazole is soluble can be used. However, considering the price, volatility at room temperature, toxicity, etc., lower alcohol solvents such as isopropyl alcohol and ethanol Is preferred.
The addition amount of 2-methylimidazole, the concentration of the solution to be applied, the reaction temperature, and the reaction time are appropriately adjusted according to the type of base material and conductive fine particles used, the thickness of the wiring to be formed, and the like.

After the reaction, it is washed with a solvent to remove excess 2-methylimidazole remaining on the surface as an unreacted substance, and then 2-methyl through a bond formed by a reaction between an epoxy group and an amino group of 2-methylimidazole. An imidazole monomolecular film 15 is formed.
The silver fine particles 31 having the monomolecular film 33 of the second film compound formed on the surface of the glass substrate 11 on which the monomolecular film 15 of 2-methylimidazole was formed were obtained. The dispersion is applied and then heated to bond and fix the silver fine particles 31 to the surface of the glass substrate 11 through a bond formed by a coupling reaction between an epoxy group and an imino group derived from 2-methylimidazole. A single-layer wiring 1 having a silver fine particle layer is manufactured.
The heating temperature is preferably 100 to 200 ° C. When the heating temperature is less than 100 ° C., it takes a long time for the coupling reaction to proceed, and when it exceeds 200 ° C., the decomposition reaction of the monomolecular films 13 and 33 having an epoxy group and the monomolecular film 15 of 2-methylimidazole. As a result, a uniform single-layer wiring 1 cannot be obtained.

After the reaction, the silver fine particles 31 that are not bonded and fixed to the surface of the glass substrate 11 are removed by washing with a solvent such as water or alcohol.

In the present embodiment, 2-methylimidazole is used as a coupling agent, but any imidazole derivative represented by the following chemical formula 7 can be used.

Specific examples of the imidazole derivative represented by Chemical Formula 7 include those shown in the following (31) to (38).
(31) 2-Methylimidazole (R ₂ = Me, R ₄ = R ₅ = H)
(32) 2-Undecylimidazole (R ₂ = C ₁₁ H ₂₃ , R ₄ = R ₅ = H)
(33) 2-Pentadecylimidazole (R ₂ = C ₁₅ H ₃₁ , R ₄ = R ₅ = H)
(34) 2-methyl-4-ethylimidazole _{(R 2 = Me, R 4} = Et, R 5 = H)
(35) 2-Phenylimidazole (R ₂ = Ph, R ₄ = R ₅ = H)
(36) 2-phenyl-4-ethylimidazole _{(R 2 = Ph, R 4} = Et, R 5 = H)
(37) 2-phenyl-4-methyl-5-hydroxymethylimidazole _{(R 2 = Ph, R 4} = Me, R 5 = CH 2 OH)
(38) 2-Phenyl-4,5-bis (hydroxymethyl) imidazole (R ₂ = Ph, R ₄ = R ₅ = CH ₂ OH)
Me, Et, and Ph represent a methyl group, an ethyl group, and a phenyl group, respectively.

In addition to imidazole derivatives, heterocyclic compounds containing two or more nitrogen such as mercaptotriazole, melamine, isocyanuric acid, triazine, barbituric acid, paravanic acid, uracil, thymine and the like can be used. Furthermore, an imidazole-metal complex such as an imidazole-copper complex may be used.

In addition, compounds such as acid anhydrides such as phthalic anhydride and maleic anhydride, and phenol derivatives such as dicyandiamide and novolak, which are used as a coupling agent for epoxy resins, may be used as a coupling agent. In this case, an imidazole derivative may be used as a catalyst in order to accelerate the coupling reaction.

In this embodiment, the case of using a film compound having an epoxy group as a functional group is described. However, when a film compound having an amino group or an imino group as a functional group is used, a coupling reactive group is used. A coupling agent having 2 or 3 or more epoxy groups or 2 or 3 or more isocyanate groups is used. Specific examples of the compound having an isocyanate group include hexamethylene-1,6-diisocyanate, toluene-2,6-diisocyanate, and toluene-2,4-diisocyanate.
The addition amount of these diisocyanate compounds is preferably 5 to 15% by weight of the epoxidized silver fine particles as in the case of 2-methylimidazole. In this case, examples of the solvent that can be used for the production of the reaction liquid include aromatic organic solvents such as xylene.
Moreover, when using the film | membrane compound which has an imino group or an amino group, the compound which has 2 or 3 or more epoxy groups, such as ethylene glycol diglycidyl ether, can also be used as a coupling agent.
(End of process D)

Next, the laminated wiring 3 according to the second embodiment of the present invention will be described.
As shown in FIG. 1B, in the multilayer wiring 3, the silver fine particle layer is formed from the first layer to the nth layer (n is an integer of 2 or more, from the glass substrate 11 side toward the interface side with air. In the embodiment, n = 2) are sequentially stacked.

A monomolecular film 13 of a first film compound having an epoxy group at one end of the molecule is formed on the surface of the glass substrate 11, and further, the coupling between the amino group of 2-methylimidazole and the epoxy group is further formed on the surface. A monomolecular film 15 of 2-methylimidazole fixed through a bond formed by the reaction is formed.
On the surface of the silver fine particles 31 forming the first silver fine particle layer, a monomolecular film 33 of a second film compound having an epoxy group at one end of the molecule is formed.
The surface of the silver fine particles 41 forming the second silver fine particle layer has a monomolecular film 43 (a coating film) of a third film compound having an epoxy group (an example of a third functional group) at one end of the molecule. An example) is formed via a bond formed by a coupling reaction between an amino group (an example of a third coupling reactive group) of 2-methylimidazole (an example of a second coupling agent) and an epoxy group A fixed 2-methylimidazole monomolecular film 45 (an example of a coating film) is further formed.

A silver fine particle 31 forming a first silver fine particle layer, a silver fine particle 31 forming a first silver fine particle layer, and a silver fine particle 41 forming a second silver fine particle layer; In the meantime, they are bonded and fixed to each other through a bond formed by a coupling reaction between the epoxy group and the amino group or imino group of 2-methylimidazole.
As shown in FIG. 1 (b), the silver fine particles 41 having a 2-methylimidazole monomolecular film 45 formed on the surface thereof are silver fine particles 31 forming the first silver fine particle layer. Although it can be bonded to the side surface of the (epoxidized silver fine particles 34), in FIG. 1 (b), the size of the conductive fine particles is exaggerated with respect to the actual pattern size for the sake of explanation. Therefore, in practice, the pattern shape is hardly damaged by this.

As shown in FIGS. 3 (a), 3 (b), 4 (a), 5 (a), 5 (b), and 1 (b), the manufacturing method of the laminated wiring 3 is an alkoxy having an epoxy group. A solution containing a silane compound is brought into contact with the surface of the glass substrate 11 to form a bond between the alkoxysilyl group (an example of the first bonding group) and the hydroxyl group 12 on the surface of the glass substrate 11. Step A (see FIG. 3) for forming a monomolecular film 13 of the first film compound and a pattern forming process for irradiating the surface of the monomolecular film 13 of the first film compound through the mask 21 covering the pattern portion. Step B (see FIG. 4) in which the pattern formation process leaving the epoxy group only in the pattern portion 22 is performed, and the surface of the silver fine particle 31 is brought into contact with an alkoxysilane compound having an epoxy group, so that the alkoxysilyl group and the silver fine particle 31 surface As shown in FIG. 3 (b), a process C (see FIG. 5) for forming a bond with the hydroxyl group 32 to form a monomolecular film 33 of the second film compound on the surface of the silver fine particles 31 is performed. Then, 2-methylimidazole is brought into contact with the glass substrate 11 subjected to the pattern formation treatment, and selectively on the surface of the pattern portion 22 only through the bond formed by the coupling reaction between the epoxy group and the amino group. A monomolecular film 15 of 2-methylimidazole is formed, and then a glass substrate 11 on which the monomolecular film 15 of 2-methylimidazole is formed, and silver fine particles 31 on which a monomolecular film 33 of the second film compound is formed, The silver fine particles 31 are selectively fixed only on the surface of the pattern portion 22 through the bond formed by the coupling reaction between the epoxy group and the imino group, and then the silver not fixed And a step D of removing particles 31.

Further, a solution containing an alkoxysilane compound having an epoxy group is brought into contact with the surface of the silver fine particle 41 to form a bond between the alkoxysilyl group (an example of the third bonding group) and the hydroxyl group on the surface of the silver fine particle 41. Then, a monomolecular film 43 of the third film compound is formed on the surface, and then 2-methylimidazole (an example of the second coupling agent) is brought into contact with the surface of the monomolecular film 43 of the third film compound. A monomolecular film 45 (an example of a film) formed by 2-methylimidazole fixed through a bond formed by a coupling reaction between an epoxy group (an example of a third functional group) and an amino group. Further, a monomolecular film 45 of 2-methylimidazole is formed on the surface of the silver fine particles 31 formed on the surface of the step E to be formed and the monomolecular film 33 of the second film compound located on the surface of the silver fine particle layer. Shape The silver fine particles 41 having the 2-methylimidazole monomolecular film 45 formed on the surface thereof are brought into contact with the second silver fine particles 41 through a bond formed by a coupling reaction between an epoxy group and an imino group. And a step F in which the monomolecular film 33 of the film compound is bonded and fixed onto the silver fine particle layer of the silver fine particles 31 formed on the surface, and then the silver fine particles 41 that are not bonded and fixed are removed.

Hereinafter, the steps A to F will be described in more detail.
Since the processes A to D are the same as the manufacturing method of the single-layer wiring 1, the description thereof is omitted.

In step E, a solution containing an alkoxysilane compound having an epoxy group is brought into contact with the surface of the silver fine particles 41 to form a bond between the alkoxysilyl group and the hydroxyl groups on the surface of the silver fine particles 41, and a third is formed on the surface. A monomolecular film 43 of a film compound is formed, and then the surface of the monomolecular film 43 of the third film compound is brought into contact with 2-methylimidazole, and a bond formed by a coupling reaction between an epoxy group and an amino group Further, a monomolecular film 45 formed by 2-methylimidazole fixed via the is formed.
The concentration of 2-methylimidazole solution used, the reaction conditions, etc. are 2 on the surface of the glass substrate 11 in step D, except that the solution is not applied but the silver fine particles 41 are dispersed in the solution and heated. -Since it is the same as that of the case where the monomolecular film 15 of methylimidazole is formed, detailed description is omitted. Other coupling agents that can be used are also the same as in Step D.

In the present embodiment, a film compound having an epoxy group is used as the third film compound, but it may be the same compound as one or both of the first and second film compounds. Different compounds may be used. Furthermore, you may have a different functional group (for example, amino group) from the 1st and 2nd film | membrane compound.
(End of process E)

In step F, a monomolecular film 45 of 2-methylimidazole is formed on the surface of the silver fine particles 31 on the surface of which the monomolecular film 33 of the second film compound is located on the surface layer of the silver fine particle layer. The silver fine particles 41 on which the monomolecular film 45 of 2-methylimidazole is formed on the surface are bonded to the second film through a bond formed by a coupling reaction between the epoxy group and the imino group. The monomolecular film 33 of the compound is bonded and fixed on the silver fine particle layer of the silver fine particles 31 formed on the surface, and then the silver fine particles 41 that are not bonded and fixed are removed.
About the reaction conditions in the process F, since it is the same as that of the process E, detailed description is abbreviate | omitted.
(End of process F)

In the present embodiment, the preparation of the wiring having two silver fine particle layers has been described. When n ≧ 3, the monomolecular film 45 of 2-methylimidazole located on the surface of the silver fine particle layer is the surface. The silver fine particles 31 on which the monomolecular film 33 of the second film compound is formed are brought into contact with the surface of the silver fine particles 41 formed on the surface to form a bond by a coupling reaction between an epoxy group and an imino group. The silver fine particles 31 with the monomolecular film 33 of the film compound 2 formed on the surface are bonded and fixed onto the silver fine particle layer of the silver fine particles 41 with the monomolecular film 45 of 2-methylimidazole formed on the surface; It further includes a step G of removing the silver fine particles 31 that are not bonded and fixed. In addition, about the reaction conditions in the process G, since it is the same as that of the process E, detailed description is abbreviate | omitted.
Further, when n ≧ 4, the method further includes a step H in which the step F and the step G are alternately repeated until an n-layer silver fine particle layer is formed. Note that the process H may be completed in either the process F or the process G. For example, when n = 4, only the process F is performed once in the process H. When n = 5, the process G is performed after the process F. When n = 6, the process F is performed once more after the process G is performed.

In the present embodiment, three kinds of film compounds are used as the film compounds for forming the film covering the surface of the base material and the silver fine particles, but they may all be the same compound. Alternatively, the surface of the silver fine particles forming each layer of the base material and the silver fine particle layer may be coated with a coating of a different film compound.
In the present embodiment, 2-methylimidazole is used as the first and second coupling agents, but different coupling agents may be used. Alternatively, different coupling agents may be used between the substrate and the first silver fine particle layer and between the silver fine particle layers.

Next, a single layer wiring 2 according to a third embodiment of the present invention will be described.
As shown in FIG. 2A, the single-layer wiring 2 is a pattern-like wiring in which one silver fine particle layer in which silver fine particles 31 are arranged only on the pattern portion 22 on the surface of the glass substrate 11 is bonded and fixed.
A monomolecular film 13 of a first film compound having an epoxy group at one end of the molecule and bonded to the surface of the pattern portion at the other end is formed on the pattern portion 22 on the surface of the glass substrate 11.
A monomolecular film 33 of a second film compound having an epoxy group at one end of the molecule and bonded to the surface of the silver fine particle 31 is formed on the surface of the silver fine particle 31, and further, an epoxy group and a cup are formed on the surface. Formed by coupling reaction of 2-methylimidazole amino group (an example of the second coupling reactive group) having one amino group and imino group in the molecule, which forms a bond by ring reaction, and an epoxy group A monomolecular film 35 of 2-methylimidazole (an example of the first coupling agent) fixed through the formed bond is formed.
The glass substrate 11 and the silver fine particles 31 are mutually connected via a bond formed by a coupling reaction between an epoxy group and an amino group or imino group (an example of a first coupling reactive group) of 2-methylimidazole. Bonding is fixed.

The manufacturing method of the single-layer wiring 2 has an epoxy group as shown in FIGS. 3A, 3B, 4A, 5A, 5B, and 2A. A solution containing an alkoxysilane compound (an example of a first film compound) is brought into contact with the surface of the glass substrate 11, and an alkoxysilyl group (an example of a first bonding group) and a hydroxyl group 12 on the surface of the glass substrate 11 are contacted. A monomolecular film of the first film compound is formed through a step A (see FIG. 3) for forming a bond and forming a monomolecular film 13 of the first film compound on the surface of the glass substrate 11 and a mask 21 covering the pattern portion. Step B (see FIG. 4) in which pattern formation processing is performed in which light irradiation (irradiation of energy rays) is performed on the surface 13 and an epoxy group is left only in the pattern portion 22, and an alkoxysilane compound having an epoxy group (One of the second membrane compounds ) Is brought into contact with the surface of the silver fine particles 31, a bond is formed between the alkoxysilyl group (an example of the second bonding group) and the hydroxyl groups 32 on the surface of the silver fine particles 31, and the second Step C (see FIG. 5) for forming the monomolecular film 33 of the film compound, and first, 2-methylimidazole is brought into contact with the silver fine particles 31 on which the monomolecular film 33 of the second film compound is formed on the surface. The monomolecular film 35 of 2-methylimidazole is formed on the surface of the monomolecular film 33 of the second film compound through the bond formed by the coupling reaction between the epoxy group and the amino group, and then the pattern portion The glass substrate 11 on which the monomolecular film 13 of the first film compound is formed only on 22 and the silver fine particles 31 on which the monomolecular film 35 of 2-methylimidazole is formed are brought into contact with each other, and a cup of an epoxy group and an imino group ring Selectively fine silver particles 31 only on the surface of the pattern portion 22 is fixed via a bond formed by response, then a step D of removing the silver particles 31 which have not been fixed.

Next, a laminated wiring 4 according to a fourth embodiment of the present invention will be described.
As shown in FIG. 2 (b), in the multilayer wiring 4, the silver fine particle layer is from the first layer to the nth layer (n is an integer of 2 or more) from the glass substrate 11 side toward the interface side with air. In this embodiment, the layers are sequentially stacked up to n = 2).

A monomolecular film 13 of a first film compound having an epoxy group at one end of the molecule is formed on the surface of the glass substrate 11.
A monomolecular film 33 of a second film compound having an epoxy group at one end of the molecule is formed on the surface of the silver fine particles 31 forming the first silver fine particle layer. -A monomolecular film 35 of 2-methylimidazole fixed through a bond formed by a coupling reaction between an amino group of methylimidazole and an epoxy group is formed.
The surface of the silver fine particles 41 forming the second silver fine particle layer has third molecules having an epoxy group (an example of a first functional group) at one end of the molecule and a third bonding group at the other end. A monomolecular film 46 (an example of a coating film) of the film compound is formed.

A silver fine particle 31 forming a first silver fine particle layer, a silver fine particle 31 forming a first silver fine particle layer, and a silver fine particle 41 forming a second silver fine particle layer; In the meantime, they are bonded and fixed to each other through a bond formed by a coupling reaction between the epoxy group and the amino group or imino group of 2-methylimidazole.
As shown in FIG. 2B, the silver fine particles 41 on the surface of which the monomolecular film 46 of the third film compound is formed form the first silver fine particle layer. Although it can also be bonded to the side surface of the silver fine particle 31 on which the monomolecular film 35 of methylimidazole is formed, in FIG. 2B, for the sake of explanation, the conductive fine particle is shown with respect to the actual pattern size. Since the size of the pattern is exaggerated, the pattern shape is hardly damaged by this.

As shown in FIGS. 3 (a), 3 (b), 4 (a), 5 (a), 5 (b), and 2 (b), the manufacturing method of the laminated wiring 4 is an alkoxy having an epoxy group. A solution containing a silane compound is brought into contact with the surface of the glass substrate 11 to form a bond between the alkoxysilyl group and the hydroxyl group 12 on the surface of the glass substrate 11, and a single molecule of the first film compound is formed on the surface of the glass substrate 11. A process A (see FIG. 3) for forming the film 13 and a pattern forming process of irradiating the surface of the monomolecular film 13 of the first film compound through the mask 21 covering the pattern part, and an epoxy group only on the pattern part 22 Step B (see FIG. 4) in which pattern formation processing is performed, and an alkoxysilane compound having an epoxy group is brought into contact with the surface of the silver fine particles 31, so that the alkoxysilyl group and the hydroxyl groups 32 on the surface of the silver fine particles 31 are contacted. Step C (see FIG. 5) of forming the second film compound on the surface of the silver fine particles 31, and first, the second film compound monomolecular film 33 is formed on the surface. The silver fine particles 31 are brought into contact with 2-methylimidazole, and an epoxy group and an amino group (an example of a second coupling reactive group) are bonded to each other through the bond formed by the coupling reaction. The monomolecular film 35 of 2-methylimidazole is formed on the surface of the monomolecular film 33, and then the glass substrate 11 on which the monomolecular film 13 of the first film compound is formed only on the pattern portion 22 and the 2-methylimidazole The silver fine particles 31 on which the monomolecular film 35 is formed are brought into contact with each other, and the pattern portion 22 is bonded via a bond formed by a coupling reaction between an epoxy group and an imino group (an example of a first coupling reactive group). Selectively only the fine silver particles 31 is fixed to the surface, then and a step D of removing the silver particles 31 which have not been fixed.

Further, a solution containing an alkoxysilane compound having an epoxy group is brought into contact with the surface of the silver fine particle 41 to form a bond between the alkoxysilyl group (an example of the third bonding group) and the hydroxyl group on the surface of the silver fine particle 41. Step E of forming a monomolecular film 46 of the third film compound on the surface, and the surface of the silver fine particles 31 on the surface of which the monomolecular film 35 of 2-methylimidazole located on the surface of the silver fine particle layer is formed The silver fine particles 41 having the monomolecular film 46 of the third film compound formed on the surface are brought into contact with each other, and the bond of the third film compound is formed through the coupling formed by the coupling reaction between the epoxy group and the imino group. The silver fine particles 41 having the monomolecular film 46 formed on the surface were bonded and fixed on the silver fine particle layer of the silver fine particles 31 having the monomolecular film 35 of 2-methylimidazole formed on the surface, and then were not bonded and fixed. And a step F of removing particulates 41.

Since Steps A to F are the same as those of the single-layer wiring 1 according to the first embodiment and the multilayer wiring 3 according to the second embodiment, detailed description thereof is omitted.
Also in the manufacturing method of the laminated wiring 4, when n ≧ 3, the surface of the silver fine particles 41 on the surface of which the monomolecular film 46 of the third film compound, which is located on the surface of the silver fine particle layer, is formed on the surface. Silver fine particles 31 having a methylimidazole monomolecular film 35 formed on the surface are brought into contact with each other, and a bond is formed by a coupling reaction between an epoxy group and an imino group, whereby a monomolecular film 35 of 2-methylimidazole is formed on the surface. A step G in which the silver fine particles 31 are bonded and fixed onto the silver fine particle layer of the silver fine particles 41 on the surface of which the monomolecular film 46 of the third film compound is formed, and then the silver fine particles 31 that are not bonded and fixed are removed. In addition.
Further, when n ≧ 4, the method further includes a step H in which the step F and the step G are alternately repeated until an n-layer silver fine particle layer is formed. Note that the process H may be completed in either the process F or the process G. For example, when n = 4, only the process F is performed once in the process H. When n = 5, the process G is performed after the process F. When n = 6, the process F is performed once more after the process G is performed.

In the present embodiment, three kinds of film compounds are used as the film compounds for forming the film covering the surface of the base material and the silver fine particles, but they may all be the same compound. Alternatively, the surface of the silver fine particles forming each layer of the base material and the silver fine particle layer may be coated with a coating of a different film compound.
Moreover, in this Embodiment, although one type of coupling agent (2-methylimidazole) is used, it is each between a base material and the 1st silver fine particle layer, and between each silver fine particle layer, respectively. Different coupling agents may be used.

The single-layer wirings 1 and 3 and the multilayer wirings 2 and 4 thus obtained have an electric conductivity of about 0.1 to 0.25 × 10 ⁶ S · cm ⁻¹ . This is a value almost comparable to the electric conductivity of bulk silver (about 0.6 × 10 ⁶ S · cm ⁻¹ ). The surface of the epoxidized silver fine particles 34 forming the single-layer wirings 1 and 3 is covered with a monomolecular film 33 of a film compound having an epoxy group. It seems that there is almost no effect on sex.
Similarly, the epoxidized silver fine particles forming the laminated wirings 2 and 4 are covered with monomolecular films 33 and 43 of a film compound having an epoxy group, but the thickness is several nm at most. It is considered that the conductivity is hardly affected.

Examples of electronic components using the single-layer wirings 1 and 3 and the multilayer wirings 2 and 4 include semiconductor integrated circuits, printed boards, via conductors on multilayer boards, and transparent electrodes on touch panels. Examples of the electronic device include any electronic device using these electronic components.

Next, examples carried out for confirming the effects of the present invention will be described.

Example 1: Formation of monomolecular film of film compound having epoxy group on glass substrate surface A glass substrate was prepared and dried well after washing.
0.99 parts by weight of 3-glycidyloxypropyltrimethoxysilane (Chemical Formula 8, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.01 parts by weight of dibutyltin bisacetylacetonate (condensation catalyst) were weighed, and 100 parts by weight of this was weighed. A reaction solution was prepared by dissolving in a hexamethyldisiloxane solvent.

The reaction solution thus obtained was applied to a glass substrate and reacted in the air (relative humidity 45%) for about 2 hours.
Then, it wash | cleaned with chloroform and the excess alkoxysilane compound and dibutyltin bisacetylacetonate were removed. By this method, a monomolecular film (film thickness of about 1 nm) of a film compound having an epoxy group could be formed on the surface of the glass substrate.

Example 2: Pattern formation treatment KrF excimer laser (wavelength 248 nm, pulse width) on a monomolecular film of a film compound having an epoxy group formed on the surface of a glass substrate in Example 1 through a mask covering the pattern part to be formed 10 ns, laser intensity 0.15 J / cm ² ) was irradiated, and the monomolecular film having an epoxy group covering a portion other than the pattern portion was removed by laser ablation. Pattern formation processing could be performed by this method.

Alternatively, Irgacure® 250 ((4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate and propylene carbonate, a 3: 1 mixture, which is a cationic photopolymerization initiator, (Specialty Chemicals) diluted with MEK (methyl ethyl ketone) and applied to the surface of the monomolecular film of the film compound having an epoxy group formed on the surface of the glass substrate, and then through a mask covering the pattern portion to be formed The pattern formation treatment could also be performed by irradiating far ultraviolet rays and ring-opening polymerizing the epoxy groups of the monomolecular film having an epoxy group covering the portion other than the pattern portion.

Example 3: Formation of a monomolecular film of a film compound having an epoxy group on the surface of silver fine particles Silver fine particles having a particle diameter of about 100 nm were prepared and dried well.
0.99 parts by weight of 3-glycidyloxypropyltrimethoxysilane (Chemical Formula 8) and 0.01 parts by weight of dibutyltin bisacetylacetonate (condensation catalyst) are weighed and dissolved in 100 parts by weight of a hexamethyldisiloxane solvent. The reaction solution was prepared.

Silver fine particles were mixed in the reaction solution thus obtained and reacted in air (relative humidity 45%) for about 2 hours while stirring.
Then, it was washed with trichlene to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate. By this method, since a hydroxyl group is also present on the surface of the silver fine particles, a monomolecular film of a film compound having an epoxy group could be formed.

Example 4: Formation of a monomolecular film of 2-methylimidazole on the glass substrate surface An ethanol solution of 2-methylimidazole was applied to the surface of the glass substrate subjected to the pattern formation process in Example 2, and heated at 100 ° C. Then, the epoxy group and the amino group of 2-methylimidazole reacted to form a monomolecular film of 2-methylimidazole. Excess 2-methylimidazole was removed by washing with ethanol.

Example 5: Formation of a monomolecular film of 2-methylimidazole on the surface of silver fine particles The silver fine particles having a monomolecular film of 2-methylimidazole formed on the surface in Example 3 were dispersed in an ethanol solution of 2-methylimidazole. When heated at 100 ° C., the epoxy group and the amino group of 2-methylimidazole reacted to form a monomolecular film of 2-methylimidazole on the surface of the silver fine particles. Thereafter, excess 2-methylimidazole was removed by washing with ethanol.

Example 6: Preparation of single-layer wiring and multilayer wiring (1)
In Example 4, the ethanol dispersion of silver fine particles in which the monomolecular film of the film compound having an epoxy group was formed on the surface in Example 3 was applied to the surface of the glass substrate on which the monomolecular film of 2-methylimidazole was formed. And heated at 100 ° C. After the reaction, it was washed with ethanol to remove excess silver fine particles. The film thickness of the single-layer wiring thus obtained was 100 nm, which is almost the same as the average particle diameter of the silver fine particles, and the interference color was not observed because the uniformity was extremely high.
An ethanol dispersion of silver fine particles in which a monomethyl film of 2-methylimidazole was further formed on the surface in Example 5 was applied to the surface of the single-layer wiring obtained by laminating one silver fine particle layer. And heated at 100 ° C. After the reaction, it was washed with ethanol to remove excess silver fine particles, and a laminated wiring in which two silver fine particle layers were laminated was obtained.
Moreover, when the electrical conductivity was measured about the laminated wiring, the measured value of about 0.2 * 10 < ⁶ > S * cm <^-1> was obtained.

Example 7: Preparation of single-layer wiring and multilayer wiring (2)
On the surface of the epoxidized glass substrate subjected to pattern formation treatment in Example 2, an ethanol dispersion of silver fine particles further formed with a monomolecular film of 2-methylimidazole on the surface was applied and heated at 100 ° C. After the reaction, it was washed with water to remove excess silver fine particles.
An ethanol dispersion of silver fine particles obtained by forming a monomolecular film of 3-glycidyloxypropyltrimethoxysilane on the surface in Example 3 on the surface of the single-layer wiring obtained by laminating one silver fine particle layer. Was further applied and heated at 100 ° C. After the reaction, it was washed with water to remove excess silver fine particles, and a laminated wiring in which two silver fine particle layers were laminated was obtained. When the electrical conductivity of the laminated wiring thus obtained was also measured, a measurement value similar to that of Example 6 of about 0.2 × 10 ⁶ S · cm ⁻¹ was obtained.

Note that an electronic component and an electronic device using a substrate on which a single-layer wiring and a multilayer wiring are formed can be manufactured using a known method, and thus detailed description thereof is omitted.

(A) is explanatory drawing which represented typically the cross-section of the pattern-shaped single layer wiring which concerns on the 1st Embodiment of this invention, (b) is the pattern shape which concerns on the 2nd Embodiment of this invention It is explanatory drawing which represented typically the cross-sectional structure of this multilayer wiring. (A) is explanatory drawing which represented typically the cross-section of the pattern-shaped single layer wiring which concerns on the 3rd Embodiment of this invention, (b) is pattern shape which concerns on the 4th Embodiment of this invention. It is explanatory drawing which represented typically the cross-sectional structure of this multilayer wiring. In the manufacturing method of the patterned wiring according to the first to fourth embodiments of the present invention, the concept expanded to the molecular level to explain the step of forming the film of the first film compound on the surface of the glass substrate. It is a figure, (a) represents the cross-sectional structure of the glass substrate before reaction, (b) represents the cross-sectional structure of the glass substrate in which the monomolecular film of the film | membrane compound which has an epoxy group was formed, respectively. (A) is the conceptual diagram expanded to the molecular level in order to demonstrate the process of performing the pattern formation process in the manufacturing method of the wiring which concerns on the 1st-4th embodiment of this invention, (b) It is the conceptual diagram expanded to the molecular level in order to demonstrate the process of performing the pattern formation process which concerns on a modification. In the manufacturing method of the wiring which concerns on the 1st-4th embodiment of this invention, it is the conceptual diagram expanded to the molecular level in order to demonstrate the process of forming the film of a 2nd film compound on the surface of silver fine particles. (A) represents the cross-sectional structure of the silver fine particles before the reaction, and (b) represents the cross-sectional structure of the silver fine particles on which the monomolecular film of the film compound having an epoxy group is formed.

Explanation of symbols

1, 2: Single-layer wiring, 3, 4: Laminated wiring, 11: Glass substrate, 12: Hydroxyl group, 13: Monomolecular film of first film compound, 14: Epoxidized glass substrate, 15: 2-methylimidazole Monomolecular film, 21: mask, 22: pattern portion, 23: removed alkoxysilane compound, 24: pattern portion, 31: silver fine particles, 32: hydroxyl group, 33: monomolecular film of second film compound, 34: Epoxidized silver fine particles, 35: 2-methylimidazole monomolecular film, 41: silver fine particles, 43: monomolecular film of third film compound, 45: monomolecular film of 2-methylimidazole, 46: third film Compound monolayer

Claims (27)

A conductive wiring layer in which conductive fine particles are arranged only on the pattern portion of the surface of the base material is a pattern-like wiring in which one layer is bonded and fixed,
The pattern portion on the surface of the base material is formed with a film of a first film compound having a first functional group at one end of the molecule and bonded to the surface of the pattern portion at the other end,
A film of a second film compound having a second functional group at one end of the molecule and bonded to the surface of the conductive fine particle at the other end is formed on the surface of the conductive fine particle,
The conductive fine particles form a bond by a coupling reaction with the second functional group and at least one first coupling reactive group that forms a bond by a coupling reaction with the first functional group. Immobilization on the base material via a bond formed by a coupling reaction between a first coupling agent having at least one second coupling reactive group and the first and second functional groups Wiring characterized by being made. The wiring according to claim 1, wherein the first film compound and the second film compound are the same compound. 3. The wiring according to claim 1, wherein one or both of the coatings formed by the first and second film compounds are monomolecular films. 4. 4. The wiring according to claim 1, wherein the bond formed by the coupling reaction is N—CH ₂ CH (OH) formed by a reaction between an amino group or an imino group and an epoxy group. Wiring characterized by being a bond. The conductive fine particle layer in which conductive fine particles are arranged only on the pattern portion on the surface of the base material is from the first layer to the nth layer (n is an integer of 2 or more) from the base material side toward the air interface side. Pattern-like wiring that is sequentially stacked
The pattern portion on the surface of the base material is formed with a film of a first film compound having a first functional group at one end of the molecule and bonded to the surface of the pattern portion at the other end,
On the surface of the first layer of the conductive fine particles, a film of a second film compound having a second functional group at one end of the molecule and bonded to the surface of the conductive fine particle at the other end is formed.
The surface of the conductive fine particles forming the xth (x is an integer, 2 ≦ x ≦ n) conductive fine particle layer has a (x + 1) th functional group on the (x + 1) th film compound Covered with a coating formed by
The first layer of conductive fine particles undergoes a coupling reaction with the second functional group and at least one first coupling reactive group that forms a bond through a coupling reaction with the first functional group. The group via a bond formed by a coupling reaction between a first coupling agent having at least one second coupling reactive group that forms a bond and the first and second functional groups. Fixed on the material,
The (x−1) -th layer and the x-th layer of the conductive fine particle layer include at least one x-th coupling reactive group that forms a bond by a coupling reaction with the x-th functional group, and the (x + 1) -th layer. The x-th coupling agent having at least one (x + 1) -th coupling reactive group that forms a bond by reacting with the functional group of), and the x-th functional group and the x-th coupling. Fixed to each other via a bond formed by a coupling reaction with a reactive group and a bond formed by a coupling reaction between the (x + 1) th functional group and the (x + 1) coupling reactive group. Wiring characterized by being. 6. The wiring according to claim 5, wherein the first to (n + 1) th film compounds and the first to nth coupling agents are the same compound. The wiring according to any one of claims 5 and 6, wherein all the films formed by the first to (n + 1) th film compounds are monomolecular films. The wiring according to claim 5, wherein the bond formed by the coupling reaction is N—CH ₂ CH (OH) formed by a reaction between an amino group or an imino group and an epoxy group. Wiring characterized by being a bond. A method of manufacturing a patterned wiring in which a conductive fine particle layer in which conductive fine particles are arranged only on a pattern portion on the surface of a substrate is bonded and fixed,
A solution containing a first membrane compound having a first functional group and a first binding group at each end of the molecule is brought into contact with the surface of the substrate, and the first binding group and the surface of the substrate are contacted with each other. Forming a bond between them, and coating the surface of the substrate with a film formed by the first film compound; and
Step B of performing a pattern forming process of irradiating the surface of the coated base material with energy rays through a mask covering the pattern portion, and leaving a film formed by the first film compound only on the pattern portion;
A solution containing a second film compound having a second functional group and a second binding group at each end of the molecule is brought into contact with the surface of the conductive fine particles, and the second binding group and the surface of the conductive fine particles And forming a film formed by the second film compound on the surface of the conductive fine particles,
One or more first coupling reactive groups that form a bond by coupling reaction with the first functional group, and one that forms a bond by coupling reaction with the second functional group Alternatively, the surface of the conductive fine particles on which the first coupling agent having two or more second coupling reactive groups, the base material subjected to the pattern formation treatment, and the film of the second film compound are formed. Respectively, and a coupling reaction between the first functional group and the first coupling reactive group, and a coupling reaction between the second functional group and the second coupling reactive group. The conductive fine particle layer made of the conductive fine particles is bonded and fixed to the surface of the base material through the bonding, and then the conductive fine particles not fixed to the surface of the base material are removed. Having step D Method for manufacturing a wiring according to claim. 10. The method for manufacturing a wiring according to claim 9, wherein the pattern forming process in the step B is performed by removing a film of the first film compound other than the pattern portion using a laser ablation method. Wiring manufacturing method. 10. The method for manufacturing a wiring according to claim 9, wherein the pattern forming process in the step B is performed by converting the first functional group other than the pattern part into another functional group by irradiation with the energy beam. A method of manufacturing a wiring characterized by the above. In the manufacturing method of the wiring according to any one of claims 9 to 11, in the step D, first, the first coupling agent is brought into contact with the surface of the substrate on which the pattern forming process has been performed. A film of the first coupling agent is selectively formed only on the surface of the pattern portion through a bond formed by a coupling reaction between the first functional group and the first coupling reactive group. Subsequently, the base material on which the first coupling agent film is formed and the conductive fine particles on which the second film compound film is formed are brought into contact with each other, and the second functional group and the second functional group are brought into contact with each other. A method for producing a wiring, wherein the conductive fine particles are selectively bonded and fixed only to the surface of the pattern portion through a bond formed by a coupling reaction with a coupling reactive group. 12. The method of manufacturing a wiring according to claim 9, wherein, in the step D, first, the first coupling is formed on the surface of the conductive fine particles on which the coating film of the second film compound is formed. An agent is contacted, and a coating film of the first coupling agent is further formed on the surface through a bond formed by a coupling reaction between the second functional group and the second coupling reactive group; Next, the conductive fine particles on which the coating film of the first coupling agent is formed are brought into contact with the substrate on which the pattern forming treatment has been performed, and the first functional group and the first coupling reactive group are brought into contact with each other. A method of manufacturing a wiring, wherein the conductive fine particles are selectively bonded and fixed only to the surface of the pattern portion through a bond formed by a coupling reaction. The method for manufacturing a wiring according to any one of claims 9 to 13, wherein the first film compound and the second film compound are the same compound. 15. The method for manufacturing a wiring according to claim 9, wherein in the step A and the step C, the unreacted first and second film compounds are washed away, and the substrate and the substrate A method of manufacturing a wiring, wherein the coating film formed by each of the first and second film compounds on the surface of the conductive fine particle is a monomolecular film. 13. The method of manufacturing a wiring according to claim 12, wherein the conductive fine particle layer is formed on the base material from the first layer to the nth layer (n is 2 or more) from the base material side toward the interface with the air. A method of manufacturing wiring that is sequentially stacked up to an integer),
A solution containing a third film compound having a third functional group and a third binding group at each end of the molecule is brought into contact with the surface of the conductive fine particle, and the third binding group and the surface of the conductive fine particle A bond between the first and second conductive particles, and a film of the third film compound is formed on the surface of the conductive fine particles, and then the surface of the conductive fine particles on which the film of the third film compound is formed, Contacting a second coupling agent having a second coupling reactive group and one or more third coupling reactive groups that form a bond through a coupling reaction with the third functional group The surface of the conductive fine particles on which the film of the third film compound is formed is formed on the surface of the conductive fine particle formed through the coupling reaction formed by the coupling reaction between the third functional group and the third coupling reactive group. Further forming a film of the second coupling agent And a step E,
The conductive fine particles on which the coating of the second film compound located on the surface layer of the conductive fine particle layer is contacted with the conductive fine particles on which the coating of the second coupling agent is formed, and the second The conductive fine particles on which the coating of the second coupling agent is formed are bonded to the second film compound through a bond formed by a coupling reaction between the functional group of the second coupling reactive group and the second coupling reactive group. A step F of bonding and fixing on the conductive fine particles on which the film is formed, and then removing the conductive fine particles on which the film of the second coupling agent that has not been bonded and fixed is formed,
In the case of n ≧ 3, contact is made with the conductive fine particles on which the coating of the second film compound is formed on the surface of the conductive fine particles having the coating of the second coupling agent located on the surface layer of the conductive fine particle layer. Conductive fine particles in which a film of the second film compound is formed through a bond formed by a coupling reaction between the second functional group and the second coupling reactive group. The method further comprises a step G of binding and fixing on the conductive fine particles on which the coating film of the coupling agent is formed, and then removing the conductive fine particles on which the coating film of the second film compound that has not been bonded and fixed is formed. In the case of n ≧ 4, the method further includes the step H of repeating the steps F and G alternately until the n conductive fine particle layers are formed. 17. The method of manufacturing a wiring according to claim 16, wherein the first to third film compounds are the same compound. 18. The method for manufacturing a wiring according to claim 16, wherein in the step E, the unreacted third film compound is removed by washing, and the third film compound is formed on the surface of the conductive fine particles. A method for producing a wiring, wherein the film formed by the film compound is a monomolecular film. 14. The method of manufacturing a wiring according to claim 13, wherein the conductive fine particle layer is formed on the substrate from the first layer to the nth layer (n is 2 or more) from the substrate side toward the interface with the air. A method of manufacturing wiring that is sequentially stacked up to an integer),
A solution containing a third film compound having the first functional group and the third binding group at both ends of the molecule is brought into contact with the surface of the conductive fine particles, and the third binding group and the conductive fine particles Forming a bond with the surface and forming a film formed by the third film compound on the surface of the conductive fine particles; and
The conductive fine particles on which the film of the first coupling agent located on the surface layer of the conductive fine particle layer is formed and the conductive fine particles on which the film of the third film compound is formed are brought into contact with each other. The conductive fine particles on which the film of the third film compound is formed are bonded to the first coupling agent through a bond formed by a coupling reaction between the functional group of the first coupling reactive group and the first coupling reactive group. And a step F of bonding and fixing on the conductive fine particles on which the film is formed, and then removing the conductive fine particles on which the film of the third film compound that has not been bonded and fixed is formed,
In the case of n ≧ 3, the conductive fine particles on which the film of the third film compound located on the surface layer of the conductive fine particle layer is formed and the conductive fine particles on which the film of the first coupling agent is formed The conductive fine particles having the first coupling agent film formed thereon are brought into contact with each other through a bond formed by a coupling reaction between the first functional group and the first coupling reactive group. A step G of bonding and fixing on the conductive fine particles on which the film of the film compound 3 is formed, and then removing the conductive fine particles on which the film of the first coupling agent that has not been fixed and fixed is removed. And when n ≧ 4, the method further comprises the step H of alternately repeating the steps F and G until the n conductive fine particle layers are formed. The method for manufacturing a wiring according to any one of claims 9 to 15, wherein the first and second film compounds are all alkoxysilane compounds, and the solution containing the first and second film compounds is: Further, as the condensation catalyst, one or more selected from the group consisting of a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate ester, and a titanate ester chelate The manufacturing method of the wiring characterized by including the compound of these. The method for manufacturing a wiring according to any one of claims 9 to 15, wherein the first and second film compounds are all alkoxysilane compounds, and the solution containing the first and second film compounds is: The wiring further comprising one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a condensation catalyst. Manufacturing method. 20. The wiring manufacturing method according to claim 16, wherein all of the first to third film compounds are alkoxysilane compounds, and the solution containing the first to third film compounds is: Further, as the condensation catalyst, one or more selected from the group consisting of a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate ester, and a titanate ester chelate The manufacturing method of the wiring characterized by including the compound of these. 20. The wiring manufacturing method according to claim 16, wherein all of the first to third film compounds are alkoxysilane compounds, and the solution containing the first to third film compounds is: The wiring further comprising one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a condensation catalyst. Manufacturing method. 23. The method for manufacturing a wiring according to claim 20, wherein the cocatalyst is further selected from the group consisting of a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound. A method for manufacturing a wiring, comprising one or two or more compounds. The method of manufacturing a wiring according to any one of claims 9 to 24, wherein the bonds formed by the coupling reaction, an amino group or imino group and N-CH ₂ CH formed by the reaction of an epoxy group (OH) Bonding method characterized by being a bond. The electronic component using the wiring of any one of Claims 1-8. The electronic device using the wiring of any one of Claims 1-8.

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