KR102304865B1 - Composition for forming conductive film, conductive film, method of manufacturing plating film, plating film and electronic device - Google Patents

Abstract

(Project) To provide a composition for forming a conductive film for forming a conductive film having low resistance and excellent adhesion to a substrate, and to provide a conductive film, a method for manufacturing a plating film, a plating film, and an electronic device.
(Solution Means) The composition for forming a conductive film used in the formation of the conductive film is (A) a metal salt containing at least one metal selected from the group consisting of Ni, Pd, Pt, Cu, Ag and Au, and at least metal particles. It prepares using one side and (B) a metaloxane compound. A coating film is formed on a substrate using the composition for forming a conductive film, heated to 250° C. or lower in the atmosphere or in a non-oxidizing atmosphere, and a conductive film is formed on the substrate to manufacture a wiring board. Further, using the composition for forming a conductive film, a coating film is formed on the transparent substrate 22 on which the first detection electrode 23 and the second detection electrode 24 are formed, and the coating film is heated to form the lead wiring 31 . ) to manufacture the touch panel 21 .

Description

A composition for forming a conductive film, a conductive film, a method for manufacturing a plating film, a plating film, and an electronic device TECHNICAL FIELD

The present invention relates to a composition for forming a conductive film, a conductive film, a method for producing a plating film, a plating film, and an electronic device.

In the field of electronic equipment having semiconductor elements and organic EL elements such as arithmetic elements, piezoelectric elements, and liquid crystal display elements, wiring boards are also called printed wiring boards, etc., and are a major component for fixing and wiring electronic components. have. Usually, the wiring of this wiring board is formed by forming a seed layer (conductive film) and performing plating.

As a composition for forming such an electrically conductive film, what contains metal microparticles|fine-particles and/or a metal salt as a metal raw material of an electrically conductive film is known.

Specifically, in the technique disclosed by Patent Document 1 and Patent Document 2, copper formate used as a raw material and an amine are combined to realize the production of fine-grained copper particles.

Moreover, in patent document 3, copper film formation is implement|achieved with the composition which combined the copper salt and the amine. In patent document 4, copper film formation is implement|achieved with the composition which combined copper formate and an amine. In patent document 5, it implement|achieves with the composition which combined copper formate and an alkanolamine.

And in patent document 6 and patent document 7, copper film formation is implement|achieved with the composition containing noble metal microparticles|fine-particles, a copper salt, a reducing agent, and a monoamine.

Japanese Laid-Open Patent Publication No. 2008-13466 Japanese Laid-Open Patent Publication No. 2008-31104 Japanese Laid-Open Patent Publication No. 2004-162110 Japanese Laid-Open Patent Publication No. 2005-2471 Japanese Laid-Open Patent Publication No. 2010-242118 Japanese Laid-Open Patent Publication No. 2011-34749 Japanese Laid-Open Patent Publication No. 2011-34750

Although studies have been actively made on a composition containing fine metal particles or a metal salt for forming a conductive film, each technique has a problem to be solved.

Specifically, in the case of a technique for forming a conductive film using a composition containing metal microparticles, it was difficult to completely fuse the metal microparticles by simple, relatively low-temperature sintering. Therefore, in the electrically conductive film obtained after sintering, there existed a problem that the electrical resistance characteristic at the time of comparing with bulk metal, ie, low resistance (low electrical resistance) cannot be implement|achieved.

Further, in the technique of the dispersion composition using the metal fine particles or the technique of the composition using the metal salt described above, there was a problem that sufficient adhesion between the conductive film and the substrate was not obtained when the conductive film was formed on the substrate.

For example, in the case of a touch panel, the conductive film on a board|substrate may be pressed by a user's touch operation, and distortion may generate|occur|produce in a board|substrate. Therefore, high adhesiveness with a board|substrate is calculated|required so that the conductive film which forms patterns, such as wiring, may not peel off by such external influence.

However, in the prior art, it was difficult to realize both the low resistance and the conductive film excellent in adhesion to the substrate compatible.

An object of the present invention is to provide a composition for forming a conductive film for forming a conductive film having low resistance and excellent adhesion to a substrate, a conductive film, a method for producing a plating film using the conductive film, a plating film, and an electronic device.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. As a result, it discovered that the said subject could be solved with the composition for conductive film formation, a conductive film, the manufacturing method of a plating film, a plating film, and an electronic device which have the following structures, and came to complete this invention.

That is, the present invention relates to the following [1] to [10].

[1] A metal salt (A1) and a metal particle (A2) containing at least one metal selected from the group consisting of Ni, Pd, Pt, Cu, Ag and Au as the component (A) serving as a metal raw material for the conductive film ) and at least one metal atom selected from the group consisting of Ti, Zr, Sn, Si and Al, in the main chain, a metaloxane compound (B) comprising a composition for forming a conductive film.

[2] The composition for forming a conductive film according to the above [1], wherein the metal salt (A1) is a carbonate containing a metal selected from the group consisting of Cu, Ag and Ni.

[3] The composition for forming a conductive film according to [2], wherein the carbonate is at least one selected from the group consisting of copper formate, silver formate and nickel formate.

[4] The composition for forming a conductive film according to [1], wherein the metal particles (A2) have an average particle diameter of 5 nm to 100 nm and contain a metal selected from the group consisting of Cu, Ag and Ni.

[5] Among the above [1] to [4], wherein the content of the component (B) is 20% by mass to 80% by mass with respect to 100% by mass of the total mass of the component (A) and the component (B). The composition for forming a conductive film according to any one of them.

[6] The composition for forming a conductive film according to any one of the above [1] to [5], further comprising (C) an amine compound.

[7] A conductive film formed using the composition for forming a conductive film according to any one of [1] to [6].

[8] A method for producing a plating film, wherein plating is further performed on the conductive film according to [7] above.

[9] A plating film produced by the method for producing a plating film according to the above [8].

[10] An electronic device comprising a wiring board having the plating film according to [9] above.

ADVANTAGE OF THE INVENTION According to this invention, the composition for conductive film formation which forms the electrically conductive film which is low resistance and is excellent in adhesiveness with a board|substrate is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a top view which shows an example of the touch panel of embodiment of this invention.
FIG. 2 is a cross-sectional view taken along line B-B' of FIG. 1 .

(Form for implementing the invention)

The composition for forming a conductive film of the present invention does not necessarily use hydrogen gas, which has been conventionally used abundantly, in the heat treatment of the coating film for forming the conductive film. If an environment excluding an oxidizing atmosphere such as atmospheric air is defined as a non-oxidizing atmosphere, the composition for forming a conductive film according to the embodiment of the present invention can form a conductive film having a desired resistance property by heating even in a non-oxidizing atmosphere. can For example, by heating the coating film in an atmosphere using nitrogen gas, argon gas, helium gas, or the like, it is possible to form a low-resistance conductive film excellent in adhesion to the substrate. Moreover, the composition for conductive film formation of embodiment of this invention can form a low-resistance conductive film excellent in adhesiveness with a board|substrate by heating even in an oxidizing atmosphere, such as air|atmosphere.

The composition for forming a conductive film of the present invention can form a uniformly uniform planar conductive film on a substrate and, by combining with an appropriate coating method, directly form a patterned conductive film constituting wiring, electrodes, terminals, etc. It can be formed on a substrate. In the present invention, the term "conductive film" is a concept including a patterned conductive film together with a uniform planar film made of a conductive material such as metal. That is, patterns such as metal wiring and metal electrodes are also included in the "conductive film" of the present invention. Similarly, a "film" may be used as a concept including a pattern.

In this invention, a "wiring board" is not limited only to the wiring board known as the above-mentioned printed wiring board. In the present invention, the "wiring board" includes all of the boards in which the patterned conductive film is formed on the board and which comprises wirings, electrodes, terminals, and the like. For example, in the present invention, the "wiring board" includes a substrate for constituting a piezoelectric element, a semiconductor element such as a liquid crystal display element, an organic EL element, etc. in addition to the printed wiring board described above. That is, as a substrate for constituting them, a substrate on which a patterned conductive film is formed on the substrate and constituting wirings, electrodes, terminals, and the like is included.

In the following description, conductive electrically conductive members called wirings, electrodes, terminals, etc. included in the wiring board are collectively referred to as wirings for convenience.

<Composition for forming a conductive film>

The composition for forming a conductive film according to an embodiment of the present invention comprises Ni (nickel), Pd (palladium), Pt (platinum), Cu (copper), Ag (silver) and At least one of a metal salt (A1) and a metal particle (A2) containing at least one metal selected from the group consisting of Au (gold), and Ti (titanium), Zr (zirconium), Sn (tin), Si It is a composition containing the metaloxane compound (B) which has in a principal chain at least 1 sort(s) of metal atom selected from the group which consists of (silicon) and Al (aluminum), and is a reduction-reaction type|mold composition for conductive film formation.

The composition for forming a conductive film of the present invention can contain (C) an amine compound, a solvent, and the like in addition to the above components.

Hereinafter, each component of the composition for conductive film formation of this embodiment is demonstrated.

[(A) component]

The composition for forming a conductive film of an embodiment of the present invention contains, as component (A), at least one metal selected from the group consisting of Ni, Pd, Pt, Cu, Ag and Au, which is a metal raw material for the conductive film. contains at least one of a metal salt (A1) and a metal particle (A2). Among these, a metal salt (A1) is preferable at the point which is low resistance and can form the electrically conductive film excellent in adhesiveness with a board|substrate.

The component (A) is preferably at least one of a metal salt and metal particles containing at least one metal selected from the group consisting of Cu, Ag and Ni from the viewpoint of forming a low-resistance conductive film at a lower manufacturing cost.

[Metal salt (A1)]

The said metal salt (A1) is a metal salt which consists of a metal ion, and at least one of inorganic anionic species and organic anionic species.

Examples of the copper-containing metal salt (A1) include copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, copper 2-methylbutyrate, copper 2-ethylbutyrate, copper valerate, copper isovalerate, Copper salts with alicyclic carboxylic acids, such as copper pivalate, copper hexanoate, copper heptanoate, copper octanoate, copper 2-ethylhexanoate, and copper nonanoate, dicarboxylic acids, such as copper malonate, copper succinate, and copper maleate Reducing power of copper salts with aromatic carboxylic acids, such as copper salts with copper salts, copper benzoate and copper salicylates, copper formate, copper hydroxyacetate, copper glyoxylate, copper lactate, copper oxalate, copper stannate, copper malate, copper citrate, etc. Copper carbonates, such as a copper salt with the carboxylic acid which has, and the hydrate of the said copper salt;

and acetylacetonate copper, ethyl acetoacetate copper, 1,1,1-trimethylacetylacetonate copper, 1,1,1,5,5,5-hexamethylacetylacetonate copper, 1,1,1-trifluoro Acetylacetone derivatives or acetoacetic acid ester derivatives per copper atom, such as copper roacetylacetonate and 1,1,1,5,5,5-hexafluoroacetylacetonate copper, are complexed in a ratio of 1 to 2 molecules. salt;

can be heard

Among these, copper acetate, copper trifluoroacetate, copper propionate, copper butyrate, copper isobutyrate, 2-methylbutyrate, copper pivalate, copper formate from the viewpoint of solubility and the ability to form a low-resistance conductive film , copper hydroxyacetate, copper glyoxylate, copper oxalate, copper acetylacetonate, copper ethyl acetoacetate, 1,1,1-trifluoroacetylacetonate copper and 1,1,1,5,5,5 - Hexafluoroacetylacetonate copper and these hydrates are preferable, and copper formate and copper formate hydrate are more preferable.

Examples of the silver-containing metal salt (A1) include silver carbonates such as silver acetate, silver formate, silver benzoate, silver citrate, silver lactate, silver trifluoroacetate and silver oxalate;

Silver nitrate, silver oxide, silver acetylacetone, ethyl silver acetoacetate, silver bromate, silver bromide, silver carbonate, silver chloride, silver fluoride, silver iodate, silver iodide, silver nitrite, silver perchlorate, silver phosphate, silver sulfate, and silver sulfide.

Among these, as a silver-containing metal salt (A1), a silver carbon salt is preferable at the point which can form a low-resistance conductive film, silver acetate, silver formate, and silver oxalate are more preferable, and silver formate is still more preferable.

Nickel carbonates, such as nickel acetate, nickel formate, and nickel oxalate, are mentioned as metal salt (A1) containing nickel. Among these, nickel formate is preferable at the point which can form a low-resistance conductive film.

The purity of the metal salt (A1) is usually 90% or more, preferably 95% or more.

A metal salt (A1) may be used by 1 type, and may use 2 or more types together.

The composition for conductive film formation of this invention WHEREIN: The content rate of a metal salt (A1) is 1 mass % - 70 mass % normally, Preferably they are 5 mass % - 50 mass %.

[Metal Particles (A2)]

Examples of the metal particles (A2) include metal particles containing at least one metal selected from the group consisting of Ni, Pd, Pt, Cu, Ag, and Au.

Among these, metal particles containing one or more metals selected from the group consisting of Ag, Cu and Ni are preferable from the viewpoint of cost, availability, and the ability to form a low-resistance conductive film.

The average particle diameter of a metal particle (A2) is the range of 5 nm - 100 nm normally. If the average particle diameter of a metal particle (A2) is the said range, the composition for electroconductive film formation excellent in storage stability can be obtained.

As a measuring method of the average particle diameter of a metal particle (A2), three arbitrary places are selected from the visual field observed with the transmission electron microscope (TEM), and it image|photographs at the most suitable magnification for particle size measurement. It can be obtained by selecting 100 particles that are thought to exist the most from each obtained photograph, measuring the diameter with a measuring instrument such as a ruler, dividing the measurement magnification to calculate the particle diameter, and arithmetic average of these values .

The purity of the metal particles (A2) is usually 95% or more, preferably 99% or more.

A metal particle (A2) may be used by 1 type, and may use 2 or more types together.

As a content rate of a metal particle (A2), it is 1 mass % - 70 mass % normally, Preferably they are 5 mass % - 50 mass %.

[Metaloxane Compound (B)]

A metaloxane compound (B) is a compound which has a metal-oxygen-metal bond in a principal chain. The metaloxane compound can be obtained, for example, by hydrolytic condensation of a compound represented by the following formula (a):

(In the formula (a), M represents a metal selected from the group consisting of Ti, Zr, Sn, Si and Al, and R ^a is an organic group having 1 to 8 carbon atoms or a ligand;

R ^b is a hydrolysable group;

n is the valence of M, which is a metal, and x is an integer from 0 to (n-1)).

Since the metaloxane compound (B) is hardly volatilized during heating during the formation of the conductive film, the conductive film formed from the composition for forming the conductive film of the present invention can stably exhibit excellent adhesion to the substrate.

^{Examples of the organic group having 1 to 8 carbon atoms represented by R a} in the formula (a) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an acetylacetonate ligand having 2 to 20 carbon atoms. Part or all of the hydrogen atoms of the alkyl group and the cycloalkyl group may be substituted with other groups.

Examples of the aforementioned alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, an i-propyl group and a butyl group are preferable from a viewpoint of the easiness of hydrolysis.

Examples of the aforementioned cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

In the formula (a), as the ligand represented by R ^a, it may be mentioned acetylacetonate diketonates anions such as anion, carboxylate anion, ammonia, amines, ketones, alcohols, carbon monoxide and the like.

In the formula (a), the ^{hydrolyzable group represented by R b} is a non-catalyst, heating within a temperature range of from room temperature (about 25° C.) to about 100° C. in the presence of excess water to generate a hydroxyl group indicates a possible group.

Examples of the formulas (a), a hydrolysable group represented by R ^b, for example, there may be mentioned an alkoxy group, an aryloxy group, a halogen atom, an acetoxy group, an isocyanate group, and the like. Among these, an alkoxy group is preferable, and a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are more preferable.

Examples of the compound represented by the formula (a) include tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetraethoxy titanium, tetramethoxy titanium, tetra-i-propoxy zirconium, tetra- metal compounds substituted with four hydrolyzable groups, such as n-butoxyzirconium, tetraethoxyzirconium, and tetramethoxyzirconium;

Methyltrimethoxytitanium, methyltriethoxytitanium, methyltri-i-propoxytitanium, methyltributoxyzirconium, ethyltrimethoxyzirconium, ethyltriethoxyzirconium, ethyltri-i-propoxyzirconium, ethyltri Butoxyzirconium, butyltrimethoxytitanium, phenyltrimethoxytitanium, naphthyltrimethoxytitanium, phenyltriethoxytitanium, naphthyltriethoxytitanium, aminopropyltrimethoxytitanium, aminopropyltriethoxyzirconium, 2- 1 such as (3,4-epoxycyclohexyl)ethyltrimethoxyzirconium, γ-glycidoxypropyltrimethoxyzirconium, 3-isocyanopropyltrimethoxyzirconium, and 3-isocyanopropyltriethoxyzirconium a metal compound substituted with two non-hydrolysable groups and three hydrolysable groups;

Triethoxymono(acetylacetonate)titanium, tri-n-propoxymono(acetylacetonate)titanium, tri-i-propoxymono(acetylacetonate)titanium, di-i-propoxybis(acetylacetonate) ) titanium compounds such as titanium and di-n-butoxybis(acetylacetonate)titanium;

Triethoxymono(acetylacetonate)zirconium, tri-n-propoxymono(acetylacetonate)zirconium, tri-i-propoxymono(acetylacetonate)zirconium, di-i-propoxybis(acetylacetonate) ) zirconium compounds such as zirconium and di-n-butoxybis(acetylacetonate)zirconium;

metal compounds substituted with two non-hydrolysable groups and two hydrolysable groups, such as dimethyldimethoxytitanium, diphenyldimethoxytitanium, and dibutyldimethoxyzirconium;

3 non-hydrolyzable groups, such as trimethylmethoxytitanium, triphenylmethoxytitanium, tributylmethoxytitanium, tri(3-methacryloxypropyl)methoxyzirconium, and tri(3-acryloxypropyl)methoxyzirconium, and 1 The metal compound etc. which were substituted by the hydrolysable group of four are mentioned.

Among these, as a compound represented by said formula (a), the metal compound substituted by four hydrolysable groups is preferable, and tetra-i- propoxy titanium and tetra-n-butoxy titanium are more preferable.

In the synthesis of the metaloxane compound (B), the amount of the compound represented by the formula (a) to be used is preferably 50 mol% to 100 mol% of the compound represented by the formula (a) with respect to all the hydrolyzable metal compounds to be used. and 80 mol% to 100 mol% are more preferable. When the compound represented by said formula (a) is less than 50 mol%, there exists a possibility that the metaloxane compound of the characteristic desired as (B) component of the composition for conductive film formation of this embodiment may not be obtained.

The method of hydrolysis-condensing the compound represented by said Formula (a) can be performed by a well-known method.

As a content rate of the metaloxane compound which is (B) component in the composition for conductive film formation of embodiment of this invention, 20 mass % - 80 with respect to 100 mass % of the total of (A) component and (B) component It is mass %, 30 mass % - 70 mass % are preferable, and 40 mass % - 60 mass % are more preferable. When the composition for conductive film formation of this embodiment contains the metaloxane compound which is (B) component in the said specific range, the electrically conductive film of embodiment of this invention excellent in adhesiveness with a board|substrate can be obtained.

[(C) amine compound]

The composition for electroconductive film formation of embodiment of this invention can contain the amine compound (C) other than (A) component and (B) component.

As an amine compound (C), the compound represented by the following general formula (1), the following general formula (2), and the following general formula (3) is mentioned.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. R ³ represents a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an amino group, a dimethylamino group, or a diethylamino group.

In the general formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. R ⁷ represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group. R ⁸ represents an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. However, when R ⁵ and R ⁶ are hydrogen atoms, R ⁸ represents other than a methyl group and an ethyl group.

In the general formula (3), R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. R ¹¹ represents a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group. R ¹² and R ¹³ each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.

^{Examples of groups R 1} and R ² contained in the amine compound represented by the general formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hep as a linear alkyl group other than a hydrogen atom. tyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group etc. are mentioned, As a branched thing, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group , neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group and the like. Examples of the alicyclic hydrocarbon group include cyclo A hexyl group and a cyclopentyl group are mentioned.

Then, the above general formula (1), examples of the group R ⁴ comprises an amine compound represented by, in addition to a hydrogen atom, an amino group, a dimethylamino group and a diethylamino group, an alkyl group of a straight chain, a methyl group, an ethyl group, a propyl group, a butyl group , a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a stearyl group, and the like. tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group, etc. are mentioned. , Examples of the alicyclic hydrocarbon group include a cyclohexyl group and a cyclopentyl group.

Specific examples of the amine compound represented by the general formula (1) include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, and undecyl. Amine, dodecylamine, stearylamine, isopropylamine, sec-butylamine, isobutylamine, tert-butylamine, isopentylamine, neopentylamine, tert-pentylamine, 1-ethylpropylamine, 1,1 -Dimethylpropylamine, 1,2-dimethylpropylamine, 1,1,2-trimethylpropylamine, 1,2,2-trimethylpropylamine, 1,3-dimethylbutylamine, neopentylamine, 1,5-dimethyl Hexylamine, 2-ethylhexylamine, 4-heptylamine, 2-heptylamine, cyclohexylamine, cyclopentylamine, ethylenediamine, N-methylethylenediamine, N,N'-dimethylethylenediamine, N,N,N ',N'-tetramethylethylenediamine, N-ethylethylenediamine, N,N'-diethylethylenediamine, 1,3-propanediamine, N,N'-dimethyl-1,3-propanediamine, 1,4 -Butanediamine, N,N'-dimethyl-1,4-butanediamine, 1,5-pentanediamine, N,N'-dimethyl-1,5-pentanediamine, 1,6-hexanediamine, N,N' -Dimethyl-1,6-hexanediamine, etc. are mentioned.

^{Examples of groups R 5} and R ⁶ contained in the amine compound represented by the general formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hep as a linear alkyl group other than a hydrogen atom. tyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group etc. are mentioned, As a branched thing, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group , neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group and the like. Examples of the alicyclic hydrocarbon group include cyclo A hexyl group and a cyclopentyl group are mentioned.

And, the general formula (2), examples of the group R ^8, including the appearing amine compound, an alkyl group of a straight chain, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, hexyl group, heptyl group, octyl group, no nyl group, decyl group, undecyl group, dodecyl group, stearyl group etc. are mentioned, As a branched thing, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, tert -pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1,3- dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group, etc. are mentioned, As an alicyclic hydrocarbon group, a cyclohexyl group and a cyclopentyl group can be heard However, ^{when both R 5} and R ⁶ are hydrogen atoms, R ⁸ is other than a methyl group and an ethyl group.

As a specific example of the amine compound represented by the said General formula (2), For example, methoxy (methyl) amine, 2-methoxyethylamine, 3-methoxypropylamine, 4-methoxybutylamine, ethoxy (methyl ) Amine, 2-ethoxyethylamine, 3-ethoxypropylamine, 4-ethoxybutylamine, propoxymethylamine, 2-propoxyethylamine, 2-isopropoxypropylamine, 3-isopropoxypropyl Amine, 2-propoxypropylamine, 3-propoxypropylamine, 4-propoxybutylamine, butoxymethylamine, butoxyethylamine, 2-butoxypropylamine, 3-butoxypropylamine, 3-( 2-ethylhexyloxy)propylamine, 3-isobutoxypropylamine, 4-butoxybutylamine, oxybis(ethylamine), etc. are mentioned.

^{Examples of groups R 9} and R ¹⁰ contained in the amine compound represented by the general formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hep as a linear alkyl group other than a hydrogen atom. tyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group etc. are mentioned, As a branched thing, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group , neopentyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group group, 1,3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group and the like. Examples of the alicyclic hydrocarbon group include cyclo A hexyl group and a cyclopentyl group are mentioned.

In addition, the formula group comprising a (3) amine compounds represented by the examples of R ¹² and R ^13, an alkyl group of a straight chain, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, hexyl group, heptyl group, octyl tyl group, nonyl group, decyl group, undecyl group, dodecyl group, stearyl group etc. are mentioned, As a branched thing, isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, isopentyl group, neophene Tyl group, tert-pentyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1 , 3-dimethylbutyl group, neopentyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group, 4-heptyl group, 2-heptyl group, etc. are mentioned, As an alicyclic hydrocarbon group, a cyclohexyl group; A cyclopentyl group is mentioned.

As a specific example of the amine compound represented by the said General formula (3), aminoacetaldehyde diethyl acetal etc. are mentioned.

As content of an amine compound (C), 0.1 mass % - 99 mass % are preferable with respect to 100 mass % of all the components which the composition for conductive film formation of this embodiment contains, and 1 mass % - 90 mass % are more preferable. And 2 mass % - 70 mass % are more preferable. (C) When content of an amine compound shall be 0.1 mass % - 99 mass %, the electroconductive film which has the outstanding electroconductivity can be formed. (C) When content of an amine compound shall be 1 mass % - 90 mass %, the conductive film of a lower resistance value can be formed by heating at a lower temperature. By setting it as 2 mass % - 70 mass %, while being able to achieve electroconductive film formation of a low resistance value, the composition for electroconductive film formation excellent in productivity can be manufactured.

[solvent]

The composition for conductive film formation of this embodiment WHEREIN: It is possible to contain a solvent other than (A) component and (B) component. By containing a solvent in the composition for electroconductive film formation, viscosity adjustment of the composition for electroconductive film formation corresponding to a coating method becomes easy, and it becomes possible to form the electroconductive film of uniform physical property.

It will not specifically limit as long as it does not participate in reaction of (A) component and (B) component as a solvent. As a solvent, 1 type of liquid chosen from water, alcohols, ethers, ester, aliphatic hydrocarbons, and aromatic hydrocarbons, or 2 or more types of compatible liquid is mentioned, for example.

Examples of alcohols include methanol, ethanol, n-propyl alcohol (1-propanol), i-propyl alcohol, n-butyl alcohol (1-butanol), i-butyl alcohol, sec-butyl alcohol, pentanol, hexanol, heptane. ol, octanol, nonyl alcohol, decanol, cyclohexanol, benzyl alcohol, terpineol, and dihydroterpineol.

Examples of the ethers include hexylmethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether. Ethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- (poly)alkylene glycol alkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol dimethyl ether, and tripropylene glycol diethyl ether, tetrahydrofuran, tetrahydropyran , 1,4-dioxane, and the like.

Examples of the esters include methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, γ-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, di Propylene glycol methyl ether acetate etc. are mentioned.

Examples of the aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, tetradecane, cyclohexane, and decalin. have.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, n-propylbenzene, i-propylbenzene, n-butylbenzene, mesitylene, tetrain, chlorobenzene, and dichlorobenzene.

Among these organic solvents, ethers are particularly preferred from the viewpoint of ease of adjustment of the viscosity of the composition for forming a conductive film.

The content rate of a solvent is the range of 0 mass % - 95 mass % with respect to 100 mass % of all the components of the composition for conductive film formation of this invention normally.

[Other optional ingredients]

In addition to (A) component and (B) component mentioned above, the composition for conductive film formation of this embodiment, unless the effect of this invention is impaired WHEREIN: Other arbitrary components can be contained. As other optional components, formic acid and/or ammonium formate may be contained, and in addition, it is possible to contain a dispersant, an antioxidant, a concentration adjuster, a surface tension adjuster, a viscosity adjuster, a coating film formation aid, an adhesion aid, and the like.

Formic acid and ammonium formate, which are other optional components, have an effect of accelerating a reduction reaction when forming a conductive film from the composition for forming a conductive film of the present embodiment, and can promote the formation of a conductive film having desired resistance properties. have.

The content rate of formic acid and ammonium formate in the composition for conductive film formation of this embodiment is 0 mass % - 50 mass normally with respect to 100 mass % of all the components which the composition for conductive film formation of this invention contains. % range.

<Method for producing a composition for forming a conductive film>

The composition for forming a conductive film of the embodiment of the present invention can be prepared by uniformly mixing the above-mentioned component (A) and component (B) and, if necessary, an amine compound (C), a solvent, and other components. can

Examples of the mixing method include stirring with a stirring blade, stirring with a stirrer and a stirrer, stirring with a stirrer, a method using an ultrasonic homogenizer, a bead mill, a paint shaker, or a stirring degassing device. As mixing conditions, for example, in the case of stirring with a stirring blade, the rotational speed of a stirring blade is the range of 1 rpm - 4000 rpm normally, Preferably it is the range of 10 rpm - 2000 rpm.

<Electroconductive film and its manufacturing method>

The conductive film of the present invention can be produced using the composition for forming a conductive film of the present invention. For example, it can manufacture by the method which has the process (1) of apply|coating the composition for conductive film formation on a board|substrate, and forming the coating film of the composition for conductive film formation, and the process (2) of heating the said coating film.

In the method for producing the conductive film, when the component (A) contains a metal salt by heating the coating film of the composition for forming a conductive film of the present embodiment applied on a substrate, the metal ions of the metal salt undergo a reduction reaction to react with metal particles. create On the other hand, component (B) in the coating film suppresses aggregation of the metal particles contained as component (A) and metal particles formed from the metal salt of component (A) during heating, and at the same time, the substrate surface and the conductive film The adhesion between the conductive film and the substrate is improved by inserting it without a gap between them. As a result, it is thought that the electroconductive film of this embodiment is low-resistance, and can exhibit the outstanding adhesiveness with the board|substrate.

[Process (1)]

Examples of the substrate include low-density polyethylene resin, high-density polyethylene resin, ABS resin (acrylonitrile/butadiene/styrene copolymer and synthetic resin), acrylic resin, styrene resin, vinyl chloride resin, polyester resin (polyethylene terephthalate, polytrimethylene). resin substrates such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate), polyacetal resins, and cellulose derivatives;

Uncoated printing paper, uncoated printing paper, coated printing paper (art paper, coated paper), special printing paper, copy paper (PPC paper), unbleached wrapping paper (matte kraft paper for heavy packaging, matte kraft paper), bleached wrapping paper (bleached kraft paper) paper substrates such as paper, pure white roll paper), coated balls, chipboard and corrugated cardboard;

metal substrates such as copper, iron, silver, gold, platinum, aluminum, nickel, titanium, tantalum, cobalt, tungsten, ruthenium, and lead;

metal alloy base materials, such as duralumin and stainless steel;

non-metallic substrates such as carbon, silicon, gallium, and zirconia;

ceramic substrates such as alumina, titania, tin oxide, yttrium oxide, barium titanate, strontium titanate, sapphire, zirconia, gallium nitride, silicon nitride, titanium nitride, tantalum nitride, polysilicon, and ITO (indium tin oxide);

glass substrates such as soda glass, borosilicate glass, silica glass, quartz glass, and chalcogen glass;

can be heard

As a coating method of the composition for forming a conductive film, inkjet printing, gravure printing, flexographic printing, (silk) screen printing, relief printing, spin coating method, spray coating method, bar coating method, casting method, dip coating method, and roll A coater method is mentioned.

[Process (2)]

The heating temperature in the step (2) may be a temperature at which, when a metal salt is contained as component (A) in the composition for forming a conductive film of the present embodiment, the metal salt is reduced and unnecessary organic matter is decomposed and volatilized; Usually, it is the range of 50 degreeC - 300 degreeC, Preferably it is the range of 50 degreeC - 250 degreeC, More preferably, it is the range of 50 degreeC - 200 degreeC. When the heating temperature is within the above range, the reduction reaction of the metal salt proceeds completely, and a substrate made of an organic material can also be used.

When the heating temperature is 300° C. or less, in the prior art, there is a problem of deterioration of the properties of the conductive film due to insufficient heating. However, in the conductive film forming method of the present embodiment, it is possible to form a conductive film having a desired characteristic even under a heating condition of 300°C or lower.

The heating time in the step (2) may be appropriately selected in consideration of the type of component contained in the composition for forming a conductive film and the desired conductivity (resistance value) of the conductive film, and is usually about 200° C. or its When the following relatively low heating temperature is selected, the heating time is preferably set to about 5 minutes to 100 minutes.

<Method for manufacturing plating film and plating film>

The manufacturing method of the plating film of this invention is a method of manufacturing a plating film using the conductive film of this invention as a seed layer of a plating process.

＜Electronic equipment＞

The electronic device of the present invention is a device in which the conductive film or the plating film of the present invention is used to form a wiring board or an electrode which is incorporated as an electrode.

As a method of forming wiring with the conductive film or plating film of the present invention, for example, it can be formed by a photofabrication method.

As an electronic device, an antenna, a sensor, a capacitor|condenser, a touch panel, organic electroluminescent etc. are mentioned, for example.

Hereinafter, the touch panel illustrated as an electronic device of embodiment of this invention is demonstrated.

[Touch Panel]

A touch panel is a touch panel which has a light-transmitting insulating film formed so that the detection electrode may be covered on the board|substrate with which the detection electrode and the lead-out wiring for drawing it were formed, for example. The touch panel can be, for example, a capacitive touch panel.

Moreover, in the touch panel of embodiment of this invention, it is also possible to set it as the structure which does not form the above-mentioned insulating film.

BRIEF DESCRIPTION OF THE DRAWINGS It is a top view which shows an example of the touchscreen of embodiment of this invention.

FIG. 2 is a cross-sectional view taken along line B-B' of FIG. 1 .

As shown in FIG. 1, the touch panel 21 which is an example of this embodiment has the 1st detection electrode 23 extended in the X direction on the surface of the transparent substrate 22, and the Y direction orthogonal to the X direction. and a second detection electrode 24 extending in

The transparent substrate 22 can be a glass substrate. The transparent substrate 22 may be a resin substrate, and in that case, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene film, a polypropylene film, a polyethersulfone film, a polycarbonate film, or a polyacrylic film. , a polyvinyl chloride film, a polyimide film, a ring-opened polymer film of cyclic olefin, a film made of a hydrogenated substance thereof, or the like can be used. As thickness of the transparent substrate 22, in the case of a glass substrate, it can be set as 0.1 mm - 3 mm. In the case of a resin substrate, it can be 10 micrometers - 3000 micrometers.

A plurality of the first detection electrodes 23 and the second detection electrodes 24 are respectively arranged. And the 1st detection electrode 23 and the 2nd detection electrode 24 are arrange|positioned in the operation area of the touch panel 21 in matrix shape. The first detection electrode 23 is used to detect the coordinates in the Y direction of the touch position by the operator. The second detection electrode 24 is used to detect the coordinates in the X direction of the touch position by the operator. The first detection electrode 23 and the second detection electrode 24 are formed on the same layer on the same surface of the transparent substrate 22 . In addition, the number of the 1st detection electrode 23 and the 2nd detection electrode 24 is not limited to the example of FIG. 1, It is preferable to determine according to the size of an operation area and the required detection precision of a touch position. That is, the touch panel 21 can be configured by using a larger number or a smaller number of the first detection electrodes 23 and the second detection electrodes 24 .

As shown in FIG. 1, the 1st detection electrode 23 and the 2nd detection electrode 24 are comprised from the some electrode pad 30 of a rhombic shape, respectively. The first detection electrode 23 and the second detection electrode 24 are spaced apart from the electrode pad 30 of the second detection electrode 24 adjacent to the electrode pad 30 of the first detection electrode 23 . arranged to do At this time, the gap between the electrode pads 30 is very small enough to ensure insulation.

And the 1st detection electrode 23 and the 2nd detection electrode 24 are arrange|positioned so that the mutually intersecting part can be made small as much as possible. Then, the electrode pads 30 constituting the first detection electrode 23 and the second detection electrode 24 are disposed over the entire operation area of the touch panel 21 .

As shown in FIG. 1, although the electrode pad 30 can be made into a rhombic shape, it is not limited to such a shape, For example, it can be set as polygonal shape, such as a hexagon.

Each of the first detection electrode 23 and the second detection electrode 24 is a transparent electrode so as not to reduce the visibility of a display such as a liquid crystal display element (not shown) disposed under the touch panel 21 . desirable. Here, a transparent electrode is an electrode provided with high transmittance|permeability with respect to visible light. As the first detection electrode 23 and the second detection electrode 24, an electrode made of a transparent conductive material, such as an electrode made of ITO or an electrode made of indium oxide and zinc oxide, can be used. When the first detection electrode 23 and the second detection electrode 24 are each made of ITO, it is preferable that the thickness thereof be 10 nm to 100 nm so that sufficient conductivity can be ensured.

The formation of the first detection electrode 23 and the second detection electrode 24 can be performed using a known method, for example, a film made of a transparent conductive material such as ITO is formed using a sputtering method or the like. , it can be carried out by patterning using a photolithography method or the like.

1 and 2, the 1st detection electrode 23 and the 2nd detection electrode 24 are formed on the same surface of the transparent substrate 22, and have comprised the same layer. Therefore, the 1st detection electrode 23 and the 2nd detection electrode 24 cross|intersect at several locations in an operation area, and the intersection part 28 is formed.

In the touch panel 21 of the present embodiment, as shown in FIG. 2 , in the intersection portion 28 , one of the first detection electrode 23 and the second detection electrode 24 does not contact the other. divided so as not to That is, in the intersection portion 28, the first detection electrodes 23 are connected, but the second detection electrodes 24 extending in the left-right direction in FIG. 2 are formed separately. And in order to electrically connect the part where the 2nd detection electrode 24 stopped, the bridge electrode 32 is formed. An interlayer insulating film 29 made of an insulating material is formed between the bridge electrode 32 and the first detection electrode 23 .

As shown in FIG. 2 , the interlayer insulating film 29 formed on the first detection electrode 23 in the intersection portion 28 is made of a material excellent in light transmittance. The interlayer insulating film 29 can be formed by applying a printing method using polysiloxane, an acrylic resin, an acrylic monomer, or the like, patterning if necessary, and then curing it by heating. When formed using polysiloxane, the interlayer insulating film 29 becomes an inorganic insulating layer made _{of silicon oxide (SiO 2 ).} In the case of using an acrylic resin and an acrylic monomer, the interlayer insulating film 29 becomes an organic insulating layer made of a resin. _{When SiO 2} is used for the interlayer insulating film 29 _{, the SiO 2} film is formed only on the first detection electrode 23 at the intersection 28 by, for example, sputtering using a mask, and the interlayer An insulating film 29 may be formed.

A bridge electrode 32 is formed on the upper layer of the interlayer insulating film 29 . As described above, the bridge electrode 32 serves to electrically connect the second detection electrodes 24 interrupted at the intersection portion 28 . It is preferable that the bridge electrode 32 is formed of the material excellent in light transmittance, such as ITO. By forming the bridge electrode 32, the second detection electrode 24 can be electrically connected in the Y direction.

1 , the first detection electrode 23 and the second detection electrode 24 have a shape in which a plurality of rhombic electrode pads 30 are arranged vertically or horizontally as described above. In the first detection electrode 23 , the connecting portion positioned at the intersection 28 has a shape that is narrower than the rhombic electrode pad 30 of the first detection electrode 23 . In addition, the bridge electrode 32 is also narrower in width than the rhombic electrode pad 30, and is formed in a strip shape.

Terminals (not shown) are respectively formed at the ends of the first detection electrode 23 and the second detection electrode 24 of the touch panel 21 , and the lead-out wiring 31 is drawn out from the terminals, respectively. The lead wiring 31 can be a wiring using the conductive film of the above-described embodiment of the present invention, such as a copper film. Similarly, a terminal can also be formed using the conductive film of embodiment of this invention.

That is, the lead-out wiring 31 of the touch panel 21 and the like can be formed by using the composition for forming a conductive film according to the embodiment of the present invention described above and according to the method for forming a conductive film according to the embodiment of the present invention described above. have.

For example, by the coating method illustrated in the conductive film formation method of the embodiment of the present invention, the coating film of the composition for forming a conductive film of the present embodiment is applied to the first detection electrode 23, the second detection electrode 24, etc. It is formed on the formed transparent substrate 22, and a wiring pattern is formed. For example, a coating film is formed by direct drawing using an inkjet printing method, a gravure printing method, a gravure offset printing method, a reverse offset printing method, a flexographic printing method, a (silk) screen printing method, a relief printing method, etc. pattern can be formed.

Then, as described above, the lead wiring 31 and the like can be formed by heating in a non-oxidizing atmosphere using an inert gas such as nitrogen gas, helium gas, or argon gas in addition to the atmosphere.

In addition, as mentioned above, the heating of a coating film can be performed also in reducing atmosphere using reducing gas, such as hydrogen gas.

The outgoing wiring 31 uses a connection terminal (not shown) at an end thereof to apply a voltage to the first detection electrode 23 and the second detection electrode 24 or to detect the position of a touch operation. electrically connected to a control circuit (not shown).

1 and 2, on the surface of the transparent substrate 22 in which the 1st detection electrode 23 and the 2nd detection electrode 24 are arrange|positioned, the 1st detection electrode 23 and the 2nd detection electrode ( A light-transmitting insulating film 25 is disposed so as to cover 24 .

The insulating film 25 is patterned and formed so as to cover and protect the first detection electrode 23 and the second detection electrode 24 in the operation area of the touch panel 21 . In addition, the insulating film 25 is formed by patterning so that the connection terminals (not shown) of the ends of the lead wires 31 drawn out from the first and second detection electrodes 23 and 24 are exposed.

A radiation-sensitive resin composition can be used to form the insulating film 25 , and can be arranged on the first detection electrode 23 and the second detection electrode 24 by performing predetermined patterning.

The touch panel 21 includes an adhesive layer (not shown) made of, for example, an acrylic transparent adhesive on the surface of the transparent substrate 22 on which the first detection electrode 23 and the second detection electrode 24 are formed. It is possible to form a cover film (not shown) made of a transparent resin by using it.

The touch panel 21 having the above configuration measures the capacitance in the operation area where the first detection electrodes 23 and the second detection electrodes 24 are arranged in a matrix shape, and the touch operation of the operator's finger or the like is performed. A contact position of a finger or the like can be detected from a change in capacitance that occurs when there is. And it can put on displays, such as a liquid crystal display element and organic electroluminescent element, and can use it suitably as an input device of the display of an electronic device.

Therefore, using the conductive film of the embodiment of the present invention, such as a copper film formed by the method for forming a conductive film of the above-described embodiment of the present invention, using the composition for forming a conductive film of the embodiment of the present invention, the lead wiring is formed using the conductive film of the embodiment of the present invention. configurable. And a touch panel can be comprised using the lead-out wiring which consists of the conductive film of embodiment of this invention.

(Example)

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described more concretely based on an Example. However, the present invention is not limited to these Examples.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]

The measuring method of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is shown below.

Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) under the following conditions using a GPC column (two G2000HXL, one G3000HXL, one G4000HXL) manufactured by Tosoh Corporation.

Solvent: tetrahydrofuran (Wako Pure Chemical Industries, Ltd.)

Flow: 1.0 mL/min

Sample concentration: 1.0% by mass

Sample injection volume: 100 μL

Detector: Differential Refractometer

Standard material: monodisperse polystyrene

<Synthesis of metaloxane compound>

[Synthesis Example 1: Synthesis of methyltrimethoxysilane/phenyltrimethoxysilane polycondensate (PMPS)]

In a container with a stirrer, 24 g of propylene glycol monomethyl ether was put, followed by 39 g of methyltrimethoxysilane (MTMS) and 18 g of phenyltrimethoxysilane (PTMS), and the solution was heated until the temperature reached 60°C. . After the solution temperature reached 60°C, 0.1 g of formic acid and 19 g of ion-exchanged water were added, heated until it reached 75°C, and stored for 2 hours. After cooling to 45 degreeC, 28 g of methyl orthoformate was added as a dehydrating agent, and it stirred for 1 hour. Furthermore, the methanol generated by ion-exchange water and hydrolysis-condensation was removed by making solution temperature 40 degreeC, and evaporating, maintaining temperature. By the above, PMPS solution was obtained. The PMPS solution was 30 mass % of solid content concentration, and the weight average molecular weight (Mw) was 2000.

[Synthesis Example 2: Synthesis of titanium tetraisopropoxide polycondensate (TTIP)]

In a three-necked eggplant-type flask equipped with a rotor, a reflux condenser and a thermometer, 5.8 g of titanium tetraisopropoxide was put, dissolved in 100 ml of tetrahydrofuran (THF), and stirred at 5°C. Furthermore, after stirring what melt|dissolved 0.6 g of water in 20 ml of THF, it dripped slowly, it heated up at 66 degreeC, and was made to react for 3 hours. After cooling the reaction, it was concentrated using an evaporator to obtain a yellow viscous substance. Further, from IR and NMR, it was found that the obtained yellow viscous substance contained a titanium tetraisopropoxide polycondensate (TTIP) having an isopropoxy group in the side chain. The weight average molecular weight (Mw) was 1800.

[Synthesis Example 3: Synthesis of titanosiloxane polymer (TS)]

In a three-necked eggplant-type flask equipped with a rotor, reflux condenser, and thermometer, a solution of 12.0 g of tetraethoxysilane in 50 ml of methanol was put, and there, 1.87 g of water, 0.83 g of 6N hydrochloric acid, and 50 ml of methanol were mixed. One solution was added at 0° C., and after partial hydrolysis reaction, a solution of 18.2 g of di-i-propoxybis(acetylacetonate) titanium and 20 ml of isopropyl alcohol was added, and the solvent was refluxed at the reflux temperature for 1 hour. By reacting, a reaction mixture was obtained. After reaction cooling, it was concentrated with an evaporator to obtain a highly viscous substance composed of a titanosiloxane polymer (TS). The weight average molecular weight (Mw) was 2200.

[Synthesis Example 4: Synthesis of Zirconosiloxane Polymer (ZS)]

In a three-necked eggplant-type flask equipped with a rotor, reflux condenser and thermometer, a solution of 10.4 g of tetraethoxysilane in 50 ml of methanol was put, and there, 1.87 g of water, 0.83 g of 6N hydrochloric acid, and 50 ml of methanol were mixed. One solution was added at 0° C., and after partial hydrolysis reaction, 10.2 g of di-i-propoxybis (acetylacetonate) zirconium was added to a mixed solution of 10 ml of ethanol, and reacted for 1 hour at the reflux temperature of the solvent. , to obtain a reaction mixture. After cooling the reaction, it was concentrated with an evaporator to obtain a high-viscosity substance composed of a zirconosiloxane polymer (ZS). The weight average molecular weight (Mw) was 2500.

[Synthesis Example 5: Synthesis of di-i-propoxybis (acetylacetonate) titanium condensate (PAT)]

In a three-necked eggplant-type flask equipped with a rotor, a reflux condenser and a thermometer, 5.8 g of di-i-propoxybis(acetylacetonate)titanium was put, dissolved in 100 ml of THF, and stirred at 5°C. Furthermore, while stirring, the solution which mixed 0.5 g of water and 20 ml of THF was dripped slowly, Then, it heated up at 66 degreeC, and made it react for 3 hours. After cooling the reaction, it was concentrated using an evaporator to obtain a di-i-propoxybis(acetylacetonate)titanium condensate (PAT) as a highly viscous substance. The weight average molecular weight (Mw) was 2400.

<Synthesis of silver formate>

[Synthesis Example 6]

In the container with a stirrer, 250 g of ethanol, 8.35 g of silver acetate, and 2.3 g of formic acid were added, stirred for 5 minutes, the produced|generated deposit was wash|cleaned with ethanol, and silver formate was obtained.

<Synthesis of silver particles>

[Synthesis Example 7]

In the flask of the reaction vessel, 13.8 g (0.188 mol) of n-butylamine (BA) as an amine compound was put, cooled in an ice bath, and 5.4 g (0.118 mol) of formic acid was added dropwise while stirring to form n-butylamine (BA) and A salt of formic acid was prepared.

Next, in another flask, silver (I) oxide 21.8 g (0.094 mol), n-hexylamine (HA) 9.51 g (0.094 mol), n-octylamine (OA) 6.06 g (0.047 mol), n-dodecyl A silver oxide dispersion solution was prepared by mixing 8.71 g (0.047 mol) of an amine (DA) and performing stirring.

Then, the salt of n-butylamine (BA) and formic acid mentioned above was dripped with respect to the silver oxide dispersion solution in a flask, stirring. After dripping, the flask was heated to 30 degreeC, and black liquid was obtained by stirring for 30 minutes.

Next, after adding methanol 100g to the obtained black liquid, stirring was stopped and it left still for 1 hour. Then, the residue was isolate|separated by the gradient method, and 18.0 g of precipitates containing silver particles were obtained.

Then, it was 55 nm when the average particle diameter of the obtained silver particle was measured using the transmission electron microscope (TEM) (the Hitachi company make, H-7650). The standard deviation when 100 primary particle diameters of the particles observed in the TEM image were randomly measured was within 20 nm, and production of silver particles with an even particle diameter was confirmed in monodispersity.

<Synthesis of copper particles>

[Synthesis Example 8]

32.3 g of 1-butanol, 46.2 g of 2-ethylhexylamine (2EHA), 3.2 g of oleic acid, and 18.3 g of anhydrous copper formate were placed in the flask of the reaction vessel, stirred under a nitrogen atmosphere until a homogeneous solution, and then oil A black liquid was obtained by heating at 100 degreeC in a bath and stirring for 60 minutes.

Next, after returning the obtained black liquid to room temperature, 100 g of methanol was added, the residue was isolate|separated by the gradient method, and 10.2g of precipitation containing a copper particle was obtained.

Then, it was 43 nm, when the average particle diameter of the obtained copper particle was measured using the transmission electron microscope (TEM) (made by Hitachi, H-7650). The standard deviation when 100 primary particle diameters of the particles observed in the TEM image were randomly measured was within 20 nm, and production of copper particles with an even particle diameter was confirmed in monodispersity.

<Preparation of a composition for forming a conductive film>

In Examples 1 to 17 and Comparative Examples 1 to 8, the metal salt or metal particles of the component (A), the metaloxane compound of the component (B), and the amine compound (C) are used, and the method shown below is used. , Examples 1 to 17 and Comparative Examples 1 to 8 were prepared as compositions for forming a conductive film. Incidentally, each of the prepared compositions for forming a conductive film is referred to as a composition for forming a copper film, a composition for forming a copper nickel film, or a composition for forming a silver film based on the main metal component of the conductive film formed using the composition.

[Example 1]

4.0 g of anhydrous copper formate, 0.1 g of PTI-023 (tetra-n-butoxytitanium polycondensate (PDBT) manufactured by Gelest), and 15.9 g of n-octylamine (OA) were mixed at room temperature with a wave rotor at 50 rpm. Thus, a composition for forming a copper film was prepared.

[Example 2]

0.1 g of PTI-023 of Example 1 was replaced with 0.07 g of M silicate 51 (methyl polysilicate manufactured by Tama Chemical Industry Co., Ltd.), and the composition for forming a copper film was prepared in the same manner otherwise.

[Example 3]

0.1 g of PTI-023 of Example 1 was replaced with silicate 45 (ethyl polysilicate manufactured by Tama Chemical Industry Co., Ltd.) 0.07 g, and the composition for forming a copper film was prepared in the same manner except for that.

[Example 4]

The n-octylamine (OA) of Example 1 was replaced with 2-ethylhexylamine (2EHA), and the composition for forming a copper film was prepared in the same manner except for that.

[Example 5]

n-octylamine (OA) of Example 1 was replaced with 3-ethoxypropylamine (3EPA), and a composition for forming a copper film was prepared in the same manner other than that.

[Example 6]

0.1 g of PTI-023 　 of Example 1 was replaced with 0.3 g of the PMPS solution of Synthesis Example 1 described above, and a composition for forming a copper film was prepared in the same manner otherwise.

[Example 7]

PTI-023 of Example 1 was replaced with the titanium tetraisopropoxide polycondensate (TTIP)-containing high-viscosity substance of Synthesis Example 2 described above, and a composition for forming a copper film was prepared in the same manner otherwise.

[Example 8]

PTI-023 of Example 1 was replaced with a high-viscosity substance containing titanosiloxane polymer (TS) of Synthesis Example 3 described above, and a copper film-forming composition was prepared in the same manner except for that.

[Example 9]

PTI-023 of Example 1 was replaced with a high-viscosity substance containing zirconosiloxane polymer (ZS) of Synthesis Example 4 described above, and a composition for forming a copper film was prepared in the same manner otherwise.

[Example 10]

PTI-023 of Example 1 was replaced with a highly viscous material containing di-i-propoxybis(acetylacetonate)titanium condensate (PAT) of Synthesis Example 5 described above, except for the composition for forming a copper film was manufactured

[Example 11]

4.0 g of anhydrous copper formate of Example 1 was replaced with 5.0 g of copper formate tetrahydrate, except for that, it carried out similarly, and the composition for copper film formation was manufactured.

[Example 12]

5.0 g of silver formate, 2.5 g of butylamine (BA), 0.1 g of PTI-023 　, and 12.0 g of butanol were mixed at room temperature with a wave rotor at 50 rpm to prepare a composition for forming a silver film.

[Example 13]

Anhydrous copper formate 3.0 g, nickel formate dihydrate 1.0 g, PTI-023 　 0.1 g, and n-octylamine (OA) 15.9 g were mixed at room temperature with a wave rotor at 50 rpm to prepare a copper nickel film-forming composition did.

[Example 14]

To 5.0 g of the precipitate containing the silver particles of Synthesis Example 7 described above, 0.8 g of terpineol and 0.2 g of PTI-023 were added to prepare a paste-like composition for forming a silver film.

[Example 15]

To 7.0 g of the precipitate containing the copper particles of Synthesis Example 8, 2.7 g of terpineol, 0.3 g of SOLSPERSE J180 (manufactured by Lubrizol), and 0.3 g of PTI-023 were added, and copper in a paste state A film-forming composition was prepared.

[Example 16]

3.5 g of copper hydroxide, 0.1 g of PTI-023 , 10.7 g of 3-ethoxypropylamine, and 3.2 g of formic acid were mixed at room temperature with a wave rotor under conditions of 50 rpm to prepare a copper film-forming composition.

[Example 17]

Copper acetate 4.2 g, PTI-023 (tetra-n-butoxytitanium polycondensate (PDBT) manufactured by Gelest) 0.1 g, 3-ethoxypropylamine 10.5 g, and formic acid 3.3 g were mixed at room temperature with a wave rotor at 50 rpm. was mixed to prepare a composition for forming a copper film.

[Comparative Example 1]

4.0 g of anhydrous copper formate and 16.0 g of n-octylamine (OA) were mixed at room temperature with a wave rotor under conditions of 50 rpm to prepare a composition for forming a copper film.

[Comparative Example 2]

n-octylamine (OA) of Comparative Example 1 was replaced with 2-ethylhexylamine (2EHA), and a copper film-forming composition was prepared in the same manner except for that.

[Comparative Example 3]

n-octylamine (OA) of Comparative Example 1 was replaced with 3-ethoxypropylamine (3EPA), and a composition for forming a copper film was prepared in the same manner other than that.

[Comparative Example 4]

PTI-023 of Example 1 was replaced with tetra-n-butoxytitanium (TBT), and a composition for forming a copper film was prepared in the same manner except for that.

[Comparative Example 5]

0.1 g of PTI-023 of Example 1 was changed to 0.07 g of methyltrimethoxysilane (MTMS), and a composition for forming a copper film was prepared in the same manner except for that.

[Comparative Example 6]

PTI-023 of Example 1 was replaced with tetra-n-butoxyzirconium (TBZR), and the composition for forming a copper film was prepared in the same manner except for that.

[Comparative Example 7]

PTI-023 of Example 1 was replaced with XER-32 (metal-free nitrile-butadiene rubber (NBR) manufactured by JSR Corporation), n-octylamine (OA) was replaced with 3-ethoxypropylamine (3EPA), and the other was the same. to prepare a composition for forming a copper film.

[Comparative Example 8]

PTI-023 of Example 1 was replaced with L-SBR-820 (liquid styrene-butadiene rubber (SBR) manufactured by Kuraray Co., Ltd.), except that the composition for forming a copper film was prepared in the same manner.

<Formation of conductive film>

Using the compositions for forming a conductive film prepared in Examples 1 to 17 and Comparative Examples 1 to 8, copper films, copper nickel films, and silver films were produced as conductive films.

[Example 18: Formation of copper film and copper nickel film]

Using the compositions for forming a copper film of Examples 1 to 11, Examples 16 to 17 and Comparative Examples 1 to 8, and the composition for forming a copper nickel film of Example 13, respectively, the substrate is 90 mm long and 90 mm wide. A coating layer of 50 mm square and a film thickness of 100 μm was formed on a square-shaped alkali-free glass substrate with a bar coater. Next, using a hot plate, in a nitrogen atmosphere, the glass substrate with the above-described coating film was heat-treated at 180° C. for 10 minutes to obtain a patterned thin film having a thickness of 0.5 µm to 1.5 µm, respectively.

Moreover, using the composition for copper film formation of Example 15, except having set the heating temperature to 250 degreeC, the thin film patterned by the method similar to the above was obtained.

[Example 19: Formation of silver film]

Using the compositions for forming a silver film of Examples 12 and 14, respectively, a coating layer of 50 mm square and a film thickness of 100 μm was formed on a base material, an alkali-free glass substrate having a square shape of 90 mm in length and 90 mm in width with a bar coater. . Next, using a hot plate, the glass substrate with the above-mentioned coating film was heat-treated at 180° C. for 10 minutes in the atmosphere to obtain a patterned thin film having a thickness of 0.5 µm to 1.5 µm, respectively.

<Evaluation>

[Example 20: Evaluation of resistance characteristics]

Using the compositions for forming a conductive film of Examples 1 to 17 and Comparative Examples 1 to 8 (a composition for forming a copper film, a composition for forming a copper nickel film, and a composition for forming a silver film), it was formed in the same manner as in Examples 18 and 19. The thin film was used and their volume resistance value was evaluated as evaluation of a resistance characteristic. The volume resistance value was measured using a 4-terminal resistance measuring instrument (trade name: Model sigma-5, manufactured by NPS Corporation). The measurement result of each volume resistance value was put together in Table 1, and was shown together with the main component of the composition for conductive film formation of Examples 1-17 and Comparative Examples 1-8 used for formation of the thin film for evaluation.

[Example 21: Evaluation of Adhesion (Adhesiveness Test)]

Using the compositions for forming a conductive film of Examples 1 to 17 and Comparative Examples 1 to 8 (a composition for forming a copper film, a composition for forming a copper nickel film, and a composition for forming a silver film), it was formed in the same manner as in Examples 18 and 19. In order to evaluate adhesiveness with a board|substrate using a thin film, the adhesive test was done. The adhesive test was performed based on the tape test method of JIS-H-8504. Evaluation was performed in three steps of the following A-C.

A: When the conductive film is not attached to the adhesive side of the tape

B: When a part of the conductive film is attached to the adhesive side of the tape

C: When all of the conductive film is attached to the adhesive side of the tape

The evaluation result of adhesiveness was put together in Table 1, and was shown together with the main component of the composition for conductive film formation of Examples 1-17 and Comparative Examples 1-8 used for formation of the thin film for evaluation.

[Example 22: Thermal shock test]

Using the compositions for forming a conductive film of Examples 1 to 17 and Comparative Examples 1 to 8 (a composition for forming a copper film, a composition for forming a copper nickel film, and a composition for forming a silver film), it was formed in the same manner as in Examples 18 and 19. The thin film was installed in a thermal shock tester (TSA-72EH-W, manufactured by SPEC Co., Ltd.), and exposed in the air under an environment of (-55°C to 85°C) x 100 cycles. The sheet resistance value before and after exposure was measured with the above-mentioned 4-terminal resistance measuring device. A thing with a resistance value increase rate less than 20 % A thing and a resistance value increase rate 20 % or more and less than 100 % of thing B, and a resistance value increase rate evaluated 100 % or more things as C. An evaluation result is put together in Table 1, and is shown. In the thin films formed using the compositions for forming a copper film of Comparative Examples 7 to 8, the state of the film was poor, such as peeling after exposure in the environment described above, and the sheet resistance value could not be measured.

[Example 23: constant temperature and humidity test]

Using the compositions for forming a conductive film of Examples 1 to 17 and Comparative Examples 1 to 8 (a composition for forming a copper film, a composition for forming a copper nickel film, and a composition for forming a silver film), it was formed in the same manner as in Examples 18 and 19. The thin film was used, installed in a constant temperature and humidity tester (PR-3J, manufactured by SPEC Co., Ltd.), and exposed in the air in an environment of (85°C·85%) × 1000 hours. The sheet resistance value before and after exposure was measured with the above-mentioned 4-terminal resistance measuring device. A thing with a resistance value increase rate of less than 20 % A, a resistance value increase rate 20 % or more and less than 100 % thing B, and a resistance value increase rate evaluated 100 % or more things as C. An evaluation result is put together in Table 1, and is shown. In the thin films formed using the compositions for forming a copper film of Comparative Examples 7 to 8, peeling occurred after exposure in the environment, and the state of the film was poor, and the sheet resistance value could not be measured.

As shown in Table 1, it turned out that each conductive film of Examples 1-17 was excellent in adhesiveness with a board|substrate, and was highly reliable. On the other hand, it turned out that each electroconductive film of Comparative Examples 1-8 had low adhesiveness with a board|substrate, and also did not have favorable reliability.

From the above evaluation results, the conductive films (copper film, copper nickel film, and silver film) respectively formed using the compositions for forming a conductive film of Examples 1 to 17 showed excellent resistance properties, excellent adhesion to the substrate, and high reliability. I found it to be combined.

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, It can implement with various deformation|transformation in the range which does not deviate from the summary of this invention.

The composition for forming a conductive film of the present invention can be suitably used as a composition for forming a conductive pattern of a circuit board in the field of electronics. And the electroconductive film of this invention can be used for manufacture of electronic components etc. in the field of electronics. For example, the conductive film of this invention can be used for manufacture of wiring, a circuit board, an antenna, a sensor, an arithmetic element, and a display element.

21: touch panel
22: transparent substrate
23: first detection electrode
24: second detection electrode
25: insulating film
28: intersection
29: interlayer insulating film
30: electrode pad
31: lead-out wiring
32: bridge electrode

Claims (10)

At least one of a metal salt (A1) and a metal particle (A2) composed only of Cu as the component (A) serving as a metal raw material for the conductive film, and
A composition for forming a conductive film, comprising a metaloxane compound (B) having in a main chain at least one metal atom selected from the group consisting of Ti, Zr, Sn, Si and Al. According to claim 1,
The composition for forming a conductive film, wherein the metal salt (A1) is a carbonate of Cu. 3. The method of claim 2,
The composition for forming a conductive film, wherein the carbonate is copper formate. According to claim 1,
The said metal particle (A2) is a composition for conductive film formation whose average particle diameter is 5 nm - 100 nm. According to claim 1,
The composition for conductive film formation whose content rate of the said (B) component is 20 mass % - 80 mass % with respect to 100 mass % of the total of the said (A) component and the said (B) component. According to claim 1,
Furthermore, (C) an amine compound is contained, The composition for conductive film formation characterized by the above-mentioned. It is formed using the composition for conductive film formation in any one of Claims 1-6, The conductive film characterized by the above-mentioned. A method for producing a plating film, wherein plating is further performed on the conductive film according to claim 7 . A plating film produced by the method for manufacturing a plating film according to claim 8. An electronic device comprising a wiring board having the plating film according to claim 9 .

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